CN113044853A - Method for synthesizing nano ZSM-5 molecular sieve with high silica-alumina ratio - Google Patents
Method for synthesizing nano ZSM-5 molecular sieve with high silica-alumina ratio Download PDFInfo
- Publication number
- CN113044853A CN113044853A CN202110417478.4A CN202110417478A CN113044853A CN 113044853 A CN113044853 A CN 113044853A CN 202110417478 A CN202110417478 A CN 202110417478A CN 113044853 A CN113044853 A CN 113044853A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- zsm
- sio
- ratio
- silica
- 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.)
- Pending
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 98
- 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 98
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 41
- 239000011707 mineral Substances 0.000 claims abstract description 41
- 238000002425 crystallisation Methods 0.000 claims abstract description 34
- 230000008025 crystallization Effects 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 10
- 229910001868 water Inorganic materials 0.000 claims abstract description 10
- 239000007790 solid phase Substances 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 60
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 229910052681 coesite Inorganic materials 0.000 claims description 19
- 229910052906 cristobalite Inorganic materials 0.000 claims description 19
- 229910052682 stishovite Inorganic materials 0.000 claims description 19
- 229910052905 tridymite Inorganic materials 0.000 claims description 19
- 229910052593 corundum Inorganic materials 0.000 claims description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- 239000000741 silica gel Substances 0.000 claims description 14
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 11
- 235000012211 aluminium silicate Nutrition 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 239000011358 absorbing material Substances 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 9
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 8
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 7
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 3
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052900 illite Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000011343 solid material Substances 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 abstract description 2
- 238000011156 evaluation Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 239000012065 filter cake Substances 0.000 description 16
- 238000005303 weighing Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 9
- 239000012452 mother liquor Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- -1 polytetrafluoroethylene Polymers 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 235000019353 potassium silicate Nutrition 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000001282 organosilanes Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 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 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 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
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
Images
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
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
-
- 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 invention belongs to the field of green synthesis of molecular sieve materials, and relates to a method for synthesizing a nano-scale high-silica-alumina-ratio ZSM-5 molecular sieve by taking natural minerals as an aluminum source. The method comprises the steps of firstly performing pseudo-solid phase activation on low-silica-alumina ratio minerals, then mixing the activated minerals with alkali, water and a small amount of template agent, and performing crystallization reaction under hydrothermal conditions to obtain the product of the nano-scale ZSM-5 molecular sieve. The invention adjusts the silica-alumina ratio of the product molecular sieve by adjusting the proportion of natural minerals in the raw materials, synthesizes the nano-scale ZSM-5 molecular sieve with the silica-alumina ratio of 130 to 2800, does not need to add a chemical aluminum source, has less dosage of a template agent and short synthesis time; the raw material range of the molecular sieve material is expanded, the production cost of the molecular sieve is greatly reduced, the greenness of the molecular sieve material is remarkably improved, the synthesized nano high-silicon ZSM-5 molecular sieve material is used as a sound absorption material to be subjected to acoustic test evaluation, the sound absorption effect is remarkable, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of green synthesis of molecular sieve materials, and relates to a method for synthesizing a nano-scale high-silica-alumina-ratio ZSM-5 molecular sieve by taking natural minerals as an aluminum source.
Background
ZSM-5 is an aluminosilicate material developed by Mobil company in 1972, has a unique pore channel structure, is adjustable in acidity and high in stability in high-temperature and hydrothermal reactions, and is widely applied to the fields of petrochemical industry, fine chemical industry, environmental protection and the like. At present, the industrial synthesis method of the ZSM-5 molecular sieve is mainly a hydrothermal crystallization method, and basic starting materials comprise a silicon source, an aluminum source, alkali, water, a template agent and the like. Mixing the materials in a certain order, aging, crystallizing, filtering, washing, drying and roasting to obtain the Na-type ZSM-5 molecular sieve. The molecular sieves with different silicon-aluminum ratios have different applications, and the high-silicon aluminum ZSM-5 molecular sieve is widely applied to methanol-to-olefin adsorption separation and the like due to moderate pore channel structure, hydrophobicity and acidity.
CN1699173A discloses a method for synthesizing a small-grain ZSM-5 molecular sieve with high silica-alumina ratio. And synthesizing the small-grain high-silicon aluminum ZSM-5 molecular sieve by adopting a hydrothermal crystallization method and simultaneously adding a template agent, a seed crystal and a surfactant. The synthesis process needs to treat the aluminum salt solution and the silicate solution respectively, and the steps are complicated. The silicon source is water glass, the yield of the product is low, the addition of the surfactant and the seed crystal increases the synthesis cost, and the method is a non-green low-cost synthesis mode.
CN101898767A discloses a method for synthesizing a high-silicon ZSM-5 molecular sieve. The high-silicon ZSM-5 molecular sieve with the silicon-aluminum ratio of more than 100 is synthesized by taking water glass as a silicon source, adding an aluminum source, an organic template agent and a guiding glue and crystallizing at high temperature, and the shape part of the molecular sieve is spherical and is uniformly dispersed. The guide glue is synthesized by dissolving a silicon source with alkali liquor and aging overnight at room temperature in the presence of an amine template. The guide glue contains a large number of molecular sieve crystal nuclei, which is beneficial to increasing the nucleation rate of the molecular sieve, shortening the crystallization time, controlling the size of the product and the like. However, the synthesis of the targeting agent requires fresh synthesis, has short storage time, is not suitable for industrial application, and needs to be used together with a template agent.
CN102671693A discloses a method for synthesizing a high silica alumina ratio nano ZSM-5 molecular sieve. And (2) taking tetraethoxysilane as a silicon source, directly adding organosilane into a molecular sieve precursor aqueous solution, carrying out condensation, reflux, mixing and stirring, and carrying out crystallization, separation, drying and roasting to obtain the nano ZSM-5 molecular sieve with the silicon-aluminum ratio not lower than 30. The tetraethoxysilane is completely used as a silicon source, the organosilane is added, the cost of the raw material is high, the experimental device is additionally arranged by recycling the organosilane in a condensation reflux mode, the process is complicated, and the cost of the device is increased.
CN104386707A discloses a method for synthesizing an ultralow-nano high-silicon nano ZSM-5 molecular sieve. The silicon source is one of water glass, silica sol and white carbon black, the template agent can be amine or one of amines, the feeding silica-alumina ratio is 80-240, the precursor gel is aged for 8 h, and the ZSM-5 molecular sieve is obtained after dynamic crystallization is 40-80 h. There are problems that the silicon-aluminum ratio range is narrow and the crystal grain size is not uniform.
Sunwangman et al (informed by silicate, 34 (2015), 1121, 1126+1132) studied the synthesis process of high Si/Al ratio by using chemical reagents of water glass and aluminum sulfate as Si/Al sources by a template method, synthesized ZSM-5 molecular sieve with Si/Al ratio of 50-500, and the grain size of 200 is about 5 μm 15 μm. The raw materials are chemical reagents, so the price is high; when the silicon-aluminum ratio is higher than 200, the crystallinity is seriously reduced; its size is large compared to commercial molecular sieve ZSM-5 molecular sieve.
CN107282087A discloses a method for synthesizing a high-silicon ZSM-5 molecular sieve. The method comprises the steps of uniformly mixing liquid alkaline silicon source, aluminum source, ZSM-5 molecular sieve seed crystal, template agent, alkali, urea and water in sequence, aging for 8-24 hours and performing hydrothermal crystallization for 24-48 hours, wherein the urea is added in the stage of uniformly mixing the raw materials. The product is a flaky high-silicon ZSM-5 molecular sieve for catalyzing organic oxygen-containing compounds to prepare C3/C4Reaction of olefins. The synthesis raw materials are all chemical reagents, and the addition of urea increases the cost of the reaction.
CN107777700A discloses a method for synthesizing microporous ZSM-5 molecular sieve by using water glass and kaolin as raw materials, and the method comprises the steps of recycling crystallized mother liquor to carry out alkali treatment on the microporous molecular sieve to obtain the step pore molecular sieveThe cost is greatly saved and the green property of the preparation process is realized. But its silicon to aluminum ratio (n (SiO)2)/n(Al2O3) ) is in the range of 20-50.
CN107879358A discloses a method for synthesizing an X-type molecular sieve by using diatomite as a silicon source and a part of an aluminum source and adopting a hydrothermal method. According to the invention, diatomite and aluminum hydroxide are respectively added into a sodium hydroxide solution for dissolution, then in-situ assembly is carried out, and the X-type molecular sieve is obtained after hydrothermal crystallization.
In summary, in recent years, researchers at home and abroad have conducted a lot of research on synthesizing the ZSM-5 molecular sieve with high silica-alumina ratio, but most of the researchers still use chemical reagents, and have the disadvantages of low yield, large amount of template agent, limited improvement of silica-alumina ratio in a synthesized sample, low crystallinity when the silica-alumina ratio is greater than 300, large grain size and the like, so that the green synthesis of the nano high silica-alumina ZSM-5 molecular sieve is still a current challenge.
Disclosure of Invention
The invention aims to provide a method for synthesizing a nano ZSM-5 molecular sieve with high silica-alumina ratio in an environment-friendly way, which selects natural minerals as synthetic raw materials of the nano ZSM-5 molecular sieve with high silica-alumina ratio, widens the silica-alumina ratio range of the natural mineral synthetic molecular sieve, and can realize the controllable preparation of the grain size of the molecular sieve with environment-friendly and low cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing a nano ZSM-5 molecular sieve with high silica-alumina ratio; adding a supplementary silicon source and a small amount of template agent into natural minerals, and preparing the nano ZSM-5 molecular sieve with the silicon-aluminum ratio of 130-2800 by adopting a hydrothermal method.
The method comprises the following steps:
(1) pseudo-solid phase activation of the mineral; mixing natural minerals and NaOH uniformly, adding deionized water, kneading, extruding into wet strips, heating, activating, and crushing to obtain activated low-silica-alumina-ratio minerals;
(2) and (3) crystallization: mixing the low silicon-aluminum ratio mineral activated in the step (1), deionized water, sodium hydroxide, a supplementary silicon source and a template agent to form uniform gel, and controlling the molar ratio of the raw materials to be SiO2/Al2O3=130~2800，Na2O/SiO2=0.01~0.5，H2O/SiO2= 10-80, template agent/SiO2= 0.01-0.5; after the gel is aged, carrying out hydrothermal crystallization, cooling, centrifuging, washing the precipitate to be neutral by using deionized water, and drying to obtain solid powder;
(3) and (3) roasting the solid powder obtained in the step (2) to obtain the nano ZSM-5 molecular sieve with high silica-alumina ratio.
The natural mineral in the step (1) is one or more of rectorite, montmorillonite, kaolin, bentonite and illite; the mass ratio of the natural mineral to NaOH is 1:1.0-10, the solid material is added with 6-15% of water and kneaded, and the activation temperature is 100-400 ℃.
The preferable molar ratio of the raw materials in the step (2) is as follows: SiO 22/Al2O3=130~2800，Na2O/SiO2=0.02~0.4，H2O/SiO2= 10-50, template agent/SiO2=0.01~0.3。
In the step (2), the aging temperature is 50-80 ℃, and the aging time is 2-18 h; the crystallization temperature is 130-200 ℃, and the crystallization time is 6-96 h; the supplementary silicon source is any one of silica gel, white carbon black, ethyl orthosilicate and sodium silicate; the template agent is any one of tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetraethylammonium bromide, n-butylamine, ethylamine or hexamethylenediamine.
In the step (3), the roasting temperature is 400-700 ℃, and the roasting time is 2-6 h.
The prepared nano ZSM-5 molecular sieve with high silica-alumina ratio is used as a sound-absorbing material.
The invention has the beneficial effects that: all aluminum sources and part of silicon sources are provided by natural minerals, and the synthesized product is SiO2/Al2O3The high-silicon ZSM-5 molecular sieve with the crystallinity larger than 130 has low raw material price, small template dosage and small grain size, and the relative crystallinity thereof is 105 percent (100-).
Drawings
FIG. 1 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve prepared in example 1 of the present invention;
FIG. 2 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve prepared in example 2 of the present invention;
FIG. 3 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve prepared in example 3 of the present invention;
FIG. 4 is an SEM image of the ZSM-5 molecular sieve prepared in example 3 of the present invention at 18000 times magnification;
FIG. 5 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve prepared in example 4 of the present invention;
FIG. 6 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve prepared in example 5 of the present invention;
FIG. 7 is an SEM image of the ZSM-5 molecular sieve prepared in example 5 of the present invention at 18000 times magnification;
FIG. 8 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve prepared in example 6 of the present invention;
FIG. 9 is an X-ray diffraction (XRD) spectrum of a ZSM-5 molecular sieve prepared in example 7 of the present invention;
FIG. 10 is an X-ray diffraction (XRD) pattern of a ZSM-5 molecular sieve prepared in example 8 of the present invention.
Detailed Description
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is not intended to limit the scope of the present invention.
A method for synthesizing a nano ZSM-5 molecular sieve with high silica-alumina ratio; adding a supplementary silicon source and a small amount of template agent into natural minerals, and preparing the nano ZSM-5 molecular sieve with the silicon-aluminum ratio of 130-2800 by adopting a hydrothermal method.
The method comprises the following steps:
(1) pseudo-solid phase activation of the mineral; mixing natural minerals and NaOH uniformly, adding deionized water, kneading, extruding into wet strips, heating, activating, and crushing to obtain activated low-silica-alumina-ratio minerals;
(2) and (3) crystallization: mixing the low silicon-aluminum ratio mineral activated in the step (1), deionized water, sodium hydroxide, a supplementary silicon source and a template agent to form uniform gel, and controlling the molar ratio of the raw materials to be SiO2/Al2O3=130~2800，Na2O/SiO2=0.01~0.5，H2O/SiO2= 10-80, template agent/SiO2=0.010.5; after the gel is aged, carrying out hydrothermal crystallization, cooling, centrifuging, washing the precipitate to be neutral by using deionized water, and drying to obtain solid powder;
(3) and (3) roasting the solid powder obtained in the step (2) to obtain the nano ZSM-5 molecular sieve with high silica-alumina ratio.
The invention uses natural minerals as all aluminum sources and part of silicon sources, the supplementary silicon sources can be silica gel, white carbon black, ethyl orthosilicate and sodium silicate, the alkalinity of the system is adjusted by sulfuric acid or hydrochloric acid, a small amount of template agent is added, and the nano ZSM-5 molecular sieve with high silica-alumina ratio is obtained through hydrothermal crystallization. The silica-alumina ratio range of the natural mineral synthesized ZSM-5 molecular sieve, the application field of the synthesized molecular sieve and the raw material source are widened. Only a small amount of template agent is used, so that the synthesis cost of the molecular sieve is reduced, and the pollution discharge is reduced.
The low silicon-aluminum ratio mineral in the invention refers to a natural mineral with a silicon-aluminum molar ratio of less than 10; therefore, in the method of the invention, besides rectorite, montmorillonite, kaolin, bentonite and illite can be selected as the natural mineral with low silica-alumina ratio.
The relative crystallinity in the examples is determined according to ASTM D5758-01, with the 2 theta angle in the XRD spectrum of the product and the molecular sieve standard being 22.5-25.0oThe standard is a ZSM-5 molecular sieve (produced by southern Kaiki university catalyst works and having a Si/Al molar ratio of 130) synthesized from conventional chemical reagents, and the crystallinity thereof is defined as 100%.
Selection of minerals, solid silica gel and template in each example: the rectorite, the kaolin and the solid silica gel are all commercial products. The rectorite comprises the following main components: SiO 22In an amount of 43.2 wt.%, Al2O3The content of the kaolin is 37.2 wt.%, and the kaolin comprises the following main components: SiO 22Is 50.5 wt.%, Al2O3The content of (a) was 44.6 wt.%. SiO of solid silica gel2Content of (B) 89.2 wt%, H2The O content was 9.9 wt%.
Example 1
Activation of the mineral: weighing 60 g of mineral rectorite and 120 g of sodium hydroxide, adding 18 g of deionized water, uniformly mixing, adding into a kneader, kneading for 1 h, placing into a strip extruder, kneading for about 15 min, extruding and molding to obtain 1.5 mm wet strips, placing into a 300 ℃ oven, drying for 4h, and crushing by a crusher to obtain pseudo-solid activated rectorite.
Preparing a molecular sieve: weighing 1.39 g of activated rectorite and 0.85 g of NaOH, dissolving in 71g of deionized water, adding 3.88 g of n-butylamine, uniformly mixing, adding 17.4 g of silica gel under the condition of stirring, mixing, stirring and aging at 70 ℃ for 4 hours; pouring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, standing at 170 ℃ for crystallization for 24 hours; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; feeding n (SiO)2/Al2O3)=130。
The phase of the synthesized product is classified as ZSM-5 molecular sieve through XRD measurement, and the relative crystallinity is 102.2%.
Example 2
Activation of the mineral: weighing 60 g of mineral kaolin and 120 g of sodium hydroxide, adding 18 g of deionized water, uniformly mixing, adding into a kneader, kneading for 1 h, placing into a strip extruder, kneading for about 15 min, extruding and molding to obtain 1.5 mm wet strips, placing into a 300 ℃ oven, drying for 4h, and crushing by a crusher to obtain the kaolin subjected to pseudo-solid phase activation.
Preparing a molecular sieve: weighing 1.00 g of activated kaolin and 1.50 g of NaOH, dissolving in 71g of deionized water, adding 3.5g of tetrapropyl ammonium bromide, uniformly mixing, adding 17.48g of silica gel under the stirring condition, mixing, stirring and aging at 70 ℃ for 4 hours; pouring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, standing at 170 ℃ for crystallization for 24 hours; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; SiO 22/Al2O3=150。
The phase of the synthesized product belongs to a ZSM-5 molecular sieve through XRD determination, and the relative crystallinity is 100%.
Example 3
Activation of the mineral: weighing 60 g of mineral rectorite and 120 g of sodium hydroxide, adding 18 g of deionized water, uniformly mixing, adding into a kneader, kneading for 1 h, placing into a strip extruder, kneading for about 15 min, extruding and molding to obtain 1.5 mm wet strips, placing into a 300 ℃ oven, drying for 4h, and crushing by a crusher to obtain pseudo-solid activated rectorite.
Preparing a molecular sieve: weighing 0.68 g of activated rectorite and 2.75 g of NaOH, dissolving in 71g of deionized water, adding 3.5g of TPABr (tetrapropylammonium bromide), uniformly mixing, adding 17.54 g of silica gel under the condition of stirring, feeding, mixing and stirring at 70 ℃, and aging for 4 hours; pouring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, standing at 170 ℃ for crystallization for 48 hours; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; feeding n (SiO)2/Al2O3)=265。
The phase of the synthesized product is classified as ZSM-5 molecular sieve through XRD determination, the relative crystallinity is 101%, and the XRD pattern is shown in figure 3. The synthesized product presents a regular shape through SEM measurement, the particle size of the sample is 500-700 nm, and the SEM spectrum is shown in figure 4.
Example 4
The preparation steps of this example are the same as those of example 1, and only some of the parameters are modulated as follows:
preparing a molecular sieve: weighing 0.64 g of rectorite and 1.30 g of NaOH, dissolving in 71g of deionized water, adding 3.88 g of n-butylamine, uniformly mixing, adding 17.54 g of silica gel under the condition of stirring, mixing, stirring and aging for 4 hours at 70 ℃; pouring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, standing at 170 ℃ for crystallization for 48 hours; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; SiO 22/Al2O3=280。
The phase of the synthesized product is classified as ZSM-5 molecular sieve through XRD measurement, and the relative crystallinity is 102.5%.
Example 5
The preparation steps of this example are the same as those of example 3, and only some of the parameters are modulated as follows:
preparing a molecular sieve: weighing 0.501 g of kaolin and 1.17 g of NaOH, dissolving in 71g of deionized water, adding 3.878 g of n-butylamine, uniformly mixing, adding 17.55 g of silica gel under the condition of stirring, mixing, stirring and aging at 70 ℃ for 4 hours; pouring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, standing at 170 ℃ for crystallization for 24 hours; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; SiO 22/Al2O3=300。
The phase of the synthesized product belongs to a ZSM-5 molecular sieve through XRD determination, and the relative crystallinity is 103%. The synthesized product presents a regular shape through SEM measurement, the particle size of a sample is 700 nm, and the SEM atlas of the synthesized product is shown in figure 7.
Example 6
The preparation steps of this example are the same as those of example 1, and only some of the parameters are modulated as follows:
preparing a molecular sieve: weighing 0.36 g of rectorite and 1.89 g of NaOH, dissolving in 71g of deionized water, adding 3.5g of TPABr (tetrapropylammonium bromide), uniformly mixing, adding 17.61 g of silica gel under the condition of stirring, mixing, stirring and aging for 4 hours at 70 ℃; pouring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, standing at 170 ℃ for crystallization for 48 hours; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; SiO 22/Al2O3=500。
The phase of the synthesized product is classified as ZSM-5 molecular sieve through XRD measurement, and the relative crystallinity is 102%.
Example 7
The preparation steps of this example are the same as those of example 3, and only some of the parameters are modulated as follows:
preparing a molecular sieve: weighing 0.19 g of kaolin and 2.41 g of NaOH, dissolving in 71g of deionized water, adding 3.5g of TPABr (tetrapropylammonium bromide), uniformly mixing, adding 17.63g of silica gel under the condition of stirring, mixing, stirring and aging at 70 ℃ for 4 hours; pouring the mixture intoStanding and crystallizing for 24 hours at 170 ℃ in a stainless steel crystallization kettle with a polytetrafluoroethylene lining; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; SiO 22/Al2O3=800。
The phase of the synthesized product is classified as ZSM-5 molecular sieve through XRD measurement, and the relative crystallinity is 104%.
Example 8
The preparation steps of this example are the same as those of example 1, and only some of the parameters are modulated as follows:
preparing a molecular sieve: weighing 0.18 g of rectorite and 3.05 g of NaOH, dissolving in 71g of deionized water, adding 3.5g of TPABr (tetrapropylammonium bromide), uniformly mixing, adding 17.64 g of silica gel under the condition of stirring, mixing, stirring and aging for 4 hours at 70 ℃; pouring the mixture into a stainless steel crystallization kettle with a polytetrafluoroethylene lining, standing at 170 ℃ for crystallization for 48 hours; after crystallization is finished, cooling and filtering to obtain a filter cake and crystallized mother liquor, washing the filter cake to be neutral, drying at 120 ℃, and roasting to obtain a NaZSM-5 molecular sieve; SiO 22/Al2O3=1000。
The phase of the synthesized product is classified as ZSM-5 molecular sieve through XRD measurement, and the relative crystallinity is 105%.
Example 9
The catalyst prepared by using the natural mineral as an aluminum source in example 3 is used for preparing a sound absorbing material for a rear cavity of a loudspeaker, and the sound absorbing material is compared with a commercial sound absorbing material to test the performance, and the specific results are shown in table 1. (. DELTA.F)0The frequency of the sound absorbing material is reduced before and after sound absorption, and the loudspeaker equipment is from the new Zhenjiang Basite Material Co
According to the results in table 1, the catalyst prepared by using the natural mineral as the aluminum source in example 3 is used for preparing the sound absorbing material for the rear cavity of the loudspeaker, the frequency of the sound absorbing material is reduced by 116 Hz, and compared with the frequency of the sound absorbing material reduced by 122 Hz, the frequency of the sound absorbing material is close, and the sound absorbing performance is excellent.
Although the present invention has been described in connection with the accompanying drawings, the present invention is not limited to the above-described embodiments, which are only illustrative and not restrictive, and many modifications may be made by those skilled in the art without departing from the spirit of the present invention, within the scope of the present invention.
Claims (8)
1. A method for synthesizing a nano ZSM-5 molecular sieve with high silica-alumina ratio is characterized in that; adding a supplementary silicon source and a small amount of template agent into natural minerals, and preparing the nano ZSM-5 molecular sieve with the silicon-aluminum ratio of 130-2800 by adopting a hydrothermal method.
2. The method of claim 1, wherein: the method comprises the following steps:
(1) pseudo-solid phase activation of the mineral; mixing natural minerals and NaOH uniformly, adding deionized water, kneading, extruding into wet strips, heating, activating, and crushing to obtain activated low-silica-alumina-ratio minerals;
(2) and (3) crystallization: mixing the low silicon-aluminum ratio mineral activated in the step (1), deionized water, sodium hydroxide, a supplementary silicon source and a template agent to form uniform gel, and controlling the molar ratio of the raw materials to be SiO2/Al2O3=130~2800，Na2O/SiO2=0.01~0.5，H2O/SiO2= 10-80, template agent/SiO2= 0.01-0.5; after the gel is aged, carrying out hydrothermal crystallization, cooling, centrifuging, washing the precipitate to be neutral by using deionized water, and drying to obtain solid powder;
(3) and (3) roasting the solid powder obtained in the step (2) to obtain the nano ZSM-5 molecular sieve with high silica-alumina ratio.
3. The method of claim 2, wherein: the natural mineral in the step (1) is one or more of rectorite, montmorillonite, kaolin, bentonite and illite; the mass ratio of the natural mineral to NaOH is 1:1.0-10, the solid material is added with 6-15% of water and kneaded, and the activation temperature is 100-400 ℃.
4. The method of claim 2, wherein: the raw materials in the step (2) have the molar ratio: SiO 22/Al2O3=130~2800，Na2O/SiO2=0.02~0.4，H2O/SiO2= 10-50, template agent/SiO2=0.01~0.3。
5. The method of claim 2, wherein: in the step (2), the aging temperature is 50-80 ℃, and the aging time is 2-18 h; the crystallization temperature is 130-200 ℃, and the crystallization time is 6-96 h.
6. The method of claim 2, wherein: the silicon source supplement in the step (2) is any one of silica gel, white carbon black, ethyl orthosilicate and sodium silicate; the template agent is any one of tetrapropylammonium bromide, tetrapropylammonium hydroxide, tetraethylammonium bromide, n-butylamine, ethylamine or hexamethylenediamine.
7. The method of claim 2, wherein: in the step (3), the roasting temperature is 400-700 ℃, and the roasting time is 2-6 h.
8. Use of a nano high silica alumina ratio ZSM-5 molecular sieve prepared by the process of claim 1, wherein; the nano ZSM-5 molecular sieve with high silica-alumina ratio is used as a sound-absorbing material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110417478.4A CN113044853A (en) | 2021-04-19 | 2021-04-19 | Method for synthesizing nano ZSM-5 molecular sieve with high silica-alumina ratio |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110417478.4A CN113044853A (en) | 2021-04-19 | 2021-04-19 | Method for synthesizing nano ZSM-5 molecular sieve with high silica-alumina ratio |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113044853A true CN113044853A (en) | 2021-06-29 |
Family
ID=76520755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110417478.4A Pending CN113044853A (en) | 2021-04-19 | 2021-04-19 | Method for synthesizing nano ZSM-5 molecular sieve with high silica-alumina ratio |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113044853A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184876A (en) * | 2021-07-05 | 2021-07-30 | 山东国瓷功能材料股份有限公司 | ZSM-5 molecular sieve for sound-absorbing material, preparation method thereof and obtained product |
| CN115842214A (en) * | 2022-10-18 | 2023-03-24 | 福州大学 | High-voltage-resistant low-self-discharge diaphragm with screening effect, preparation method and application |
| CN115925437A (en) * | 2022-12-08 | 2023-04-07 | 上海绿强新材料有限公司 | Integral honeycomb molecular sieve for removing VOCs (volatile organic compounds), and preparation and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723405A (en) * | 2008-10-24 | 2010-06-09 | 中国石油大学(北京) | Method for preparing ZSM-5 molecular sieves |
| CN102671693A (en) * | 2012-05-16 | 2012-09-19 | 上海师范大学 | Nanometer ZSM-5 molecular sieve catalyst with high silica-alumina ratio and preparation method thereof |
| CN105731492A (en) * | 2016-01-28 | 2016-07-06 | 中国石油大学(华东) | Low-cost green method for synthesizing Fe-ZSM-5 molecular sieve |
| CN106185977A (en) * | 2016-06-30 | 2016-12-07 | 福州大学 | A kind of method of green syt ZSM 5 molecular sieve |
| AU2020101871A4 (en) * | 2020-08-18 | 2020-09-24 | University Of Science And Technology Beijing | A Method for Preparing ZSM-5 Zeolite by Using Solid wastes |
-
2021
- 2021-04-19 CN CN202110417478.4A patent/CN113044853A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723405A (en) * | 2008-10-24 | 2010-06-09 | 中国石油大学(北京) | Method for preparing ZSM-5 molecular sieves |
| CN102671693A (en) * | 2012-05-16 | 2012-09-19 | 上海师范大学 | Nanometer ZSM-5 molecular sieve catalyst with high silica-alumina ratio and preparation method thereof |
| CN105731492A (en) * | 2016-01-28 | 2016-07-06 | 中国石油大学(华东) | Low-cost green method for synthesizing Fe-ZSM-5 molecular sieve |
| CN106185977A (en) * | 2016-06-30 | 2016-12-07 | 福州大学 | A kind of method of green syt ZSM 5 molecular sieve |
| AU2020101871A4 (en) * | 2020-08-18 | 2020-09-24 | University Of Science And Technology Beijing | A Method for Preparing ZSM-5 Zeolite by Using Solid wastes |
Non-Patent Citations (2)
| Title |
|---|
| 周相娜等: "以低温固相碱熔活化高岭土为原料合成ZSM-5分子筛", 《工业催化》 * |
| 岳源源等: ""Mesoscale depolymerization of natural rectorite mineral via a quasi-solid-phase approach for zeolite synthesis"", 《CHEMICAL ENGINEERING SCIENCE》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184876A (en) * | 2021-07-05 | 2021-07-30 | 山东国瓷功能材料股份有限公司 | ZSM-5 molecular sieve for sound-absorbing material, preparation method thereof and obtained product |
| TWI788013B (en) * | 2021-07-05 | 2022-12-21 | 大陸商山東國瓷功能材料股份有限公司 | Zsm-5 molecular sieve for sound-absorbing material, method for preparing the same, and product obtained therefrom |
| WO2023279513A1 (en) * | 2021-07-05 | 2023-01-12 | 山东国瓷功能材料股份有限公司 | Zsm-5 molecular sieve for sound-absorbing material, preparation method therefor, and resulting product |
| CN115842214A (en) * | 2022-10-18 | 2023-03-24 | 福州大学 | High-voltage-resistant low-self-discharge diaphragm with screening effect, preparation method and application |
| CN115925437A (en) * | 2022-12-08 | 2023-04-07 | 上海绿强新材料有限公司 | Integral honeycomb molecular sieve for removing VOCs (volatile organic compounds), and preparation and application thereof |
| CN115925437B (en) * | 2022-12-08 | 2023-12-19 | 上海绿强新材料有限公司 | Integral honeycomb molecular sieve for VOCs removal and preparation and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113044853A (en) | Method for synthesizing nano ZSM-5 molecular sieve with high silica-alumina ratio | |
| CA2778370C (en) | Method of preparing zsm-5 zeolite using nanocrystalline zsm-5 seeds | |
| US9963350B2 (en) | ZSM-5 type molecular sieve synthesis method | |
| WO2015161630A1 (en) | Fezsm-5 molecular sieve and synthesis process therefor | |
| KR20150005538A (en) | Beta zeolite and method for producing same | |
| CN109701619A (en) | SSZ-13/SSZ-39 composite molecular sieves and its synthetic method | |
| WO2018205840A1 (en) | Mesoporous beta zeolite and preparation method therefor | |
| CN106219569B (en) | A method of no one step of secondary template prepares porous zeotile | |
| CN102441425B (en) | Preparation method for Y/MCM-41 composite molecular sieve | |
| CN110156040A (en) | ZSM-5 molecular sieve and preparation method thereof | |
| CN114751426A (en) | Preparation method and application of B-Al-ZSM-5 molecular sieve | |
| CN112661167B (en) | Synthesis method of nano mordenite molecular sieve and molecular sieve | |
| CN110790283A (en) | Synthesis method of mordenite with high silicon-aluminum ratio | |
| CN112591764B (en) | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof | |
| JP4488691B2 (en) | Method for producing faujasite type zeolite | |
| CN101417810A (en) | Mesoporous material and preparation method thereof | |
| TW202235370A (en) | Zsm-23 molecular sieve and preparation method therefor | |
| CN110078093B (en) | NaY molecular sieve and preparation method and application thereof | |
| CN113135578A (en) | Preparation method of silicon-germanium ISV zeolite molecular sieve | |
| CN109133089B (en) | Synthesis method of nano-scale T-shaped molecular sieve | |
| US20080182744A1 (en) | Ready-to-use seed composition and process thereof | |
| CN110683558B (en) | Synthesis method of MTT zeolite molecular sieve with short shaft morphology | |
| CN106946273B (en) | A kind of EU-1/ZSM-5 composite molecular screen and its synthetic method | |
| CN110143602A (en) | A kind of preparation method of beta-molecular sieve | |
| CN110759357B (en) | Synthesis method of zsm-35/zsm-5 eutectic 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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210629 |