CN104445255A - Preparation method of heteroatom MCM-49 zeolite molecular sieve - Google Patents
Preparation method of heteroatom MCM-49 zeolite molecular sieve Download PDFInfo
- Publication number
- CN104445255A CN104445255A CN201410740431.1A CN201410740431A CN104445255A CN 104445255 A CN104445255 A CN 104445255A CN 201410740431 A CN201410740431 A CN 201410740431A CN 104445255 A CN104445255 A CN 104445255A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- source
- solution
- mcm
- heteroatoms
- 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 58
- 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 58
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 44
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 40
- 239000010457 zeolite Substances 0.000 title claims abstract description 40
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003292 glue Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000007789 sealing Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 27
- 230000008025 crystallization Effects 0.000 claims description 24
- 230000007062 hydrolysis Effects 0.000 claims description 23
- 238000006460 hydrolysis reaction Methods 0.000 claims description 23
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004411 aluminium Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [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 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229960001866 silicon dioxide Drugs 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 239000007792 gaseous phase Substances 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical group CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 4
- 238000000034 method Methods 0.000 abstract description 22
- 239000000047 product Substances 0.000 abstract description 20
- 239000003795 chemical substances by application Substances 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000009616 inductively coupled plasma Methods 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000009415 formwork Methods 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 238000005216 hydrothermal crystallization Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical group Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing MCM-49 zeolite molecular sieve with a framework containing heteroatoms, which is characterized in that a silicon gel precursor A containing the heteroatoms is obtained by co-hydrolyzing a silicon source and a heteroatom source mixed solution by adjusting the pH value of the silicon source and the heteroatom source mixed solution; uniformly mixing water, an aluminum source and an alkali source according to a certain ratio to obtain a solution B; slowly dripping the solution B into the solution A to form uniform crystallized liquid, heating and evaporating the crystallized liquid to obtain dry glue, placing the dry glue on the upper part of a reaction kettle, placing water and a template agent on the lower part of the reaction kettle, sealing, and crystallizing at the temperature of 140-180 ℃ for 3-15 days to obtain the MCM-49 zeolite molecular sieve with the framework containing the heteroatom. The method avoids the phenomenon that the heteroatom is hydrolyzed to form oxide precipitate, has simple and easy operation, small template agent consumption, recyclability and reutilization, less environmental pollution, and high crystallinity and good repeatability of the prepared product.
Description
Technical field
The invention belongs to zeolite molecular sieve synthesis field, relate to the preparation method of a kind of skeleton containing heteroatomic MCM-49 zeolite molecular sieve.
Background technology
MCM-49 zeolite molecular sieve is a kind of zeolite molecular sieve material (US5236575) with MWW topological framework developed first by Mobil company of the U.S., it have two covers independently, mutual disconnected duct system (Science, 1994,264:1910-1912): one is aperture is
ten-ring two dimension sinusoidal duct; Two is pass through
the diameter that ten-ring opening communicates with the external world is
twelve-ring supercage.MCM-49 molecular sieve is with the pore structure of its uniqueness, good heat/hydrothermal stability and suitable acidity, at aromatic hydrocarbons, low-carbon alkene and long chain olefin alkylation (US584098, US5545788, US5973193) etc. demonstrate application prospect widely in process.
Transition metal (the Co of oxidation activity will be had, Mn, Cr, V, Ti, Fe etc.) introduce framework of molecular sieve can obtain separated from one another, the active centre of high dispersing, the special pore passage structure of molecular sieve is then for active centre provides suitable space, make it possess the oxidation-reduction quality of transition metal and the acidity of molecular sieve and shape selectivity simultaneously, make highly selective synthesize object product and become possibility, simultaneously, some heteroatoms can also strengthen the skeleton structure of molecular sieve, improve thermostability and the hydrothermal stability of molecular sieve, these advantages are all that the synthesis of poromerics and catalytic applications thereof bring new opportunity, so the synthesis of heteroatoms zeolite molecular sieve is always noticeable.Wu etc. take boric acid as structural promoter, synthesize Ti-MWW molecular sieve (J Phys ChemB first, 2001,105:2897-2905), find that Ti-MWW molecular sieve has excellent performance (J Catal to the linear olefin molecules of different size with being with in the normal olefine catalytic epoxidation of functional group, 2006,237:359-367).Vanadium ion is incorporated in the skeleton of Al-MCM-22 molecular sieve by Pastore etc., and preliminarily investigated the performance of its oxidative dehydrogenation of propane, result shows [V, Al]-MCM-22 is a kind of acid/redox dual-function catalyst (J Catal of unique properties, 2006,241:367-377).
In zeolite molecular sieve skeleton, infrared (IR) antisymmetric stretching vibration range of frequency of T-O (T=Si, Al) structure is: 1050-1150cm
-1, symmetrical stretching vibration range of frequency is: 750-820cm
-1.The people such as Szostack (J Catal, 1986,101 (2): 549-552) think, T atom in framework of molecular sieve T-O key is by after the hybrid atom MCM-41 except boron, its stretching vibration frequency is to lower wave number displacement, therefore according to the IR stretching vibration frequency of T-O key whether to lower wave number displacement, can as judging whether heteroatoms enters the evidence of zeolite molecular sieve skeleton.
Method heteroatoms being introduced zeolite molecular sieve skeleton mainly contains direct crystallization method and isomorphous substitution two-step fabrication.In the material that a kind of rear method is obtained, heteroatoms mainly concentrates on channel surfaces atomic shell, and is easily deposited as non-cage heteroatom species over a molecular sieve, causes heteroatoms skewness and easily runs off in reaction process.And by the heteroatoms zeolite molecular sieve that direct crystallization method is synthesized, heteroatoms is high uniformity distribution, and do not change molecular sieve pore passage structure, complicated aftertreatment need not be carried out, therefore there is the superiority that additive method is incomparable.
At present, the research report of the MCM-49 molecular sieve of synthesis Heteroatom doping is few, the method of conventional synthesis heteroatoms MCM-49 zeolite molecular sieve is hydrothermal crystallization method (CN1171792C), the method is normally in the basic conditions by silicon source, aluminium source, be mixed to form hydrogel by a certain percentage containing the raw material such as compound and organic formwork agent of transition metal, hydrogel puts into sealed vessel or autoclave, carries out crystallization and prepare heteroatoms MCM-49 zeolite molecular sieve under the autogenous pressure of certain temperature and water.But transition metal ion is easy to hydrolysis at a high ph and generates oxyhydroxide or oxide precipitation, makes it to carry out reacting the difficulty forming chemical bond with silicon species and increases, cause transition metal to be in fact difficult to enter zeolite framework, and finally generate oxide compound.On the other hand, adopt during hydrothermal crystallization method synthesis heteroatoms MCM-49 zeolite molecules and need to use a large amount of organic formwork agents, because organic formwork agent is expensive, had a strong impact on the preparation cost of MCM-49 molecular sieve; Meanwhile, after Zeolite synthesis, isolated a large amount of mother liquor is alkaline ammonia nitrogen waste water, and directly discharge can produce severe contamination to environment.Therefore the synthetic route that exploration one is new synthesizes heteroatoms MCM-49 zeolite molecular sieve quickly and efficiently, has very important industrial significance and huge economic benefit.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of simple skeleton containing heteroatomic MCM-49 zeolite molecular sieve.
Technical scheme of the present invention is: in building-up process, generate oxyhydroxide or hydrous oxide precipitation to effectively reduce heteroatoms because of hydrolysis, be conducive to heteroatoms and enter framework of molecular sieve, the present invention adopts the cohydrolysis preparation in acidic medium of silicon source and heteroatomic compound to contain heteroatomic silicate sol precursor, heteroatoms Me is existed with the form of Si-O-Me, and then above-mentioned precursor is mixed in the basic conditions with aluminium source, dry glue is made in heating, adopts vapor phase transfer method crystallization to obtain skeleton containing heteroatoms zeolite molecular sieve.Heteroatoms wherein proves by Infrared spectroscopy the skeleton entering zeolite molecular sieve crystal.
Technical scheme of the present invention is: a kind of preparation method of heteroatoms MCM-49 zeolite molecular sieve, and its concrete preparation process is as follows:
A, by mixture heating hydrolysis in acidic medium of silicon source and deionized water, controlling the pH value of solution is 1.0-6.0, obtains solution A; Wherein said heteroatoms source is containing the one in the oxide compound of Fe, V, Co, Cr, Ni, Mn, Ga or Zr element, muriate, nitrate, vitriol and acetate;
B, aluminium source and inorganic alkali source spent ionized water and dissolve, obtain solution B;
C, be added drop-wise in solution A by solution B, the mol ratio that mixture is always formed is: SiO
2/ Al
2o
3=20-100, M
2o/SiO
2=0.1-0.3, Me/SiO
2=0.0025-0.05, H
2o/SiO
2=15-50, wherein M is monovalent base metal ion, and Me is heteroatom elements;
D, above-mentioned reaction mixture heat drying is obtained dry glue;
E, above-mentioned xerogel is placed in reactor upper gaseous phase position, template hexamethylene imine (HMI) and water are placed in reactor lower liquid phase position according to the mixture that mass ratio 0.05-0.2: 1 forms, sealing, be warmed up to crystallization temperature, by solid product washing, centrifugal, dry, roasting after crystallization terminates, obtain skeleton containing heteroatomic MCM-49 zeolite molecular sieve.
Preferably above-mentioned silicon source is silicate, silicon sol, silicon-dioxide, tetraethoxy or methyl silicate.
Preferred described acidic medium is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrofluoric acid or careless aqueous acid.
Preferably described aluminium source is Tai-Ace S 150, aluminum chloride, sodium aluminate, aluminum nitrate, aluminum isopropylate, pseudo-boehmite or aluminium powder; Inorganic alkali source is sodium hydroxide or potassium hydroxide.
Above-mentioned raw materials is commercially available.
Hydrolysis temperature described in preferred steps a is 20-90 DEG C, and hydrolysis time is 2-24 hour; Drying temperature described in steps d is 50-100 DEG C, and time of drying is 2-24 hour; Crystallization temperature described in step e is 140-180 DEG C, and crystallization time is 3-15 days.Washing, centrifugal, dry, roasting condition routinely.
Skeleton provided by the invention is adopt direct crystallization method to be synthesized to by heteroatoms in MCM-49 zeolite molecular sieve skeleton containing heteroatomic MCM-49 zeolite molecular sieve, the results of FT-IR shows that the IR stretching vibration frequency containing its T-O key of heteroatoms MCM-49 molecular sieve of the present invention is to lower wave number displacement, can prove the skeleton entering zeolite molecular sieve containing the heteroatoms in heteroatomic MCM-49 zeolite molecular sieve at least partly provided by the invention thus.
Beneficial effect:
(1) adopt the method for cohydrolysis silicon source and metal heteroatom under weakly acidic condition to prepare gel, be conducive to heteroatoms and enter framework of molecular sieve, improve the content of metallic element in framework of molecular sieve, gained zeolite product degree of crystallinity is high, reproducible.
(2) solid-liquid separation in building-up process, decreases the consumption of organic formwork agent, and organic formwork agent is recyclable reuses, and improves single-autoclave yield rate.
Accompanying drawing explanation
Fig. 1 a, b and c are the X-ray diffractogram of comparative example 1, embodiment 1 and 2 gained sieve sample respectively.
Fig. 2 a, b and c are the infrared spectrogram of comparative example 1, embodiment 1 and 2 gained sieve sample respectively.
Embodiment
Below in conjunction with embodiment, the present invention is described further, but not thereby limiting the invention.
Comparative example 1
Get tetraethoxy 11.31g, add the 0.3M aqueous hydrochloric acid of 10.25ml wherein, the hydrolysis pH value of regulator solution, to 2.0, stirs hydrolysis 2 hours in 90 DEG C, makes solution A; 0.315g sodium hydroxide and 0.415g sodium aluminate solution are made B solution in 8.4ml deionized water, solution B is added drop-wise at leisure in solution A, stirs, the mol ratio that mixture is always formed is SiO
2: 0.125Na
2o: 0.033Al
2o
3: 20H
2o, transfers in 80 DEG C of baking ovens by gained mixture, dry 4 hours until form dry glue.By dry glue grind into powder, get the dry glue of 2g and be placed in reactor top, reactor bottom is 20g water and 2g hexamethylene imine.After reactor sealing at 158 DEG C static crystallization 5 days, obtain not containing the former powder of heteroatomic MCM-49 zeolite molecular sieve by after products therefrom washing to neutral, centrifugal, drying.Its X-ray diffraction spectrogram (XRD) is shown in Fig. 1 a, and infrared spectrum (IR) is shown in Fig. 2 a.
Embodiment 1
Get tetraethoxy 11.31g, iron nitrate 0.43g, add the 0.3M aqueous hydrochloric acid of 10.25ml wherein, the hydrolysis pH value of regulator solution, to 2.0, stirs hydrolysis 2 hours in 90 DEG C, makes solution A; 0.419g sodium hydroxide and 0.415g sodium aluminate solution are made B solution in 8.4ml deionized water, solution B is added drop-wise at leisure in solution A, stirs, the mol ratio that mixture is always formed is SiO
2: 0.15Na
2o: 0.033Al
2o
3: 0.02Fe: 20H
2o, transfers in 80 DEG C of baking ovens by gained mixture, dry 4 hours until form dry glue.By dry glue grind into powder, get the dry glue of 2g and be placed in reactor top, reactor bottom is 20g water and 2g hexamethylene imine.After reactor sealing at 158 DEG C static crystallization 7 days, by products therefrom washing to neutral, centrifugal, dry, product proves through X-ray diffraction and infrared spectrum characterization result: its product finally obtained is the MCM-49 zeolite molecular sieve of Fe2O3 doping.Its X-ray diffraction spectrogram (XRD) is shown in Fig. 1 b, and infrared spectrum (IR) is shown in Fig. 2 b.Employing inductively coupled plasma method (ICP) records the Fe/SiO in molecular sieve
2(mol ratio)=0.0135.
Embodiment 2
According to operation steps and the operational condition of embodiment 1, difference is that aluminium source is aluminum nitrate, and heteroatomic compound is chromium nitrate, and the mol ratio that mixture always forms is SiO
2: 0.3Na
2o: 0.033Al
2o
3: 0.05Cr: 25H
2o, the drying temperature preparing dry glue is 50 DEG C, and time of drying is 24 hours, and reactor bottom is 15g water and 3g hexamethylene imine, and crystallization temperature is 158 DEG C, and crystallization time is 12 days.Product proves through X-ray diffraction and infrared spectrum characterization result: its product finally obtained is the MCM-49 zeolite molecular sieve of chromium doping.Its X-ray diffraction spectrogram (XRD) is shown in Fig. 1 c, and infrared spectrum (IR) is shown in Fig. 2 c.Employing inductively coupled plasma method (ICP) records the Cr/SiO in molecular sieve
2(mol ratio)=0.0376.
Embodiment 3
According to operation steps and the operational condition of embodiment 1, difference is that silicon source is water glass, and aluminium source is Tai-Ace S 150, heteroatomic compound is vanadylic sulfate, and acid solution is sulfuric acid, and hydrolysis pH value is 4.0,20 DEG C are stirred hydrolysis 24 hours, and the mol ratio that mixture always forms is SiO
2: 0.2Na
2o: 0.01Al
2o
3: 0.01V: 35H
2o, crystallization temperature is 140 DEG C, and crystallization time is 15 days.Product characterizes through XRD and IR and proves: its product finally obtained is the MCM-49 zeolite molecular sieve of vanadium doping.Employing inductively coupled plasma method (ICP) records the V/SiO in molecular sieve
2(mol ratio)=0.0063.
Embodiment 4
According to operation steps and the operational condition of embodiment 1, difference is that silicon source is water glass, and aluminium source is aluminum isopropylate, heteroatoms source is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, and acid solution is hydrofluoric acid, and hydrolysis pH value is 3.0,20 DEG C are stirred hydrolysis 24 hours, and the mol ratio that mixture always forms is SiO
2: 0.125Na
2o: 0.017Al
2o
3: 0.0025Co: 15H
2o, crystallization temperature is 168 DEG C, and crystallization time is 3 days.Product characterizes through XRD and IR and proves: its product finally obtained is the MCM-49 zeolite molecular sieve of cobalt doped.Employing inductively coupled plasma method (ICP) records the Co/SiO in molecular sieve
2(mol ratio)=0.0019.
Embodiment 5
According to operation steps and the operational condition of embodiment 1, difference is that silicon source is methyl silicate, and heteroatoms source is zirconium white, and acid solution is acetic acid, and alkali source is KOH, and the mol ratio that mixture always forms is SiO
2: 0.2K
2o: 0.05Al
2o
3: 0.005Zr: 30H
2o, hydrolysis pH value is 3.0,40 DEG C and stirs hydrolysis 12 hours, and reactor bottom is 20g water and 1g hexamethylene imine, and crystallization temperature is 158 DEG C, and crystallization time is 10 days.Product characterizes through XRD and IR and proves: its product finally obtained is the MCM-49 zeolite molecular sieve of zirconium doping.Employing inductively coupled plasma method (ICP) records the Zr/SiO in molecular sieve
2(mol ratio)=0.0031.
Embodiment 6
According to operation steps and the operational condition of embodiment 1, difference is that silicon source is methyl silicate, and aluminium source is aluminium powder, heteroatoms source is gallium chloride, and acid solution is oxalic acid, and hydrolysis pH value is 6.0,80 DEG C are stirred hydrolysis 4 hours, and the drying temperature preparing dry glue is 100 DEG C, and time of drying is 2 hours.Crystallization temperature is 158 DEG C, and crystallization time is 12 days.Product characterizes through XRD and IR and proves: its product finally obtained is the MCM-49 zeolite molecular sieve of gallium doping.Employing inductively coupled plasma method (ICP) records the Ga/SiO in molecular sieve
2(mol ratio)=0.0117.
Embodiment 7
According to operation steps and the operational condition of embodiment 1, difference is that silicon source is silicon sol, and aluminium source is aluminum chloride, and heteroatoms source is manganous nitrate, and acid solution is nitric acid, and hydrolysis pH value is 1.0, and the mol ratio that mixture always forms is SiO
2: 0.3Na
2o: 0.02Al
2o
3: 0.04Mn: 50H
2o, the drying temperature preparing dry glue is 60 DEG C, and time of drying is 12 hours, and reactor bottom is 20g water and 4g hexamethylene imine.Crystallization temperature is 180 DEG C, and crystallization time is 10 days.Product characterizes through XRD and IR and proves: its product finally obtained is the MCM-49 zeolite molecular sieve of additive Mn.Employing inductively coupled plasma method (ICP) records the Mn/SiO in molecular sieve
2(mol ratio)=0.0296.
Embodiment 8
According to operation steps and the operational condition of embodiment 1, difference is that silicon source is silicon-dioxide, and aluminium source is pseudo-boehmite, heteroatoms source is single nickel salt, and alkali source is potassium hydroxide, and acid solution is phosphoric acid, hydrolysis pH value is 6.0,60 DEG C and stirs hydrolysis 8 hours, and the mol ratio that mixture always forms is SiO
2: 0.2K
2o: 0.02Al
2o
3: 0.02Ni: 35H
2o.Product characterizes through XRD and IR and proves: its product finally obtained is the MCM-49 zeolite molecular sieve of nickel doping.Employing inductively coupled plasma method (ICP) records the Ni/SiO in molecular sieve
2(mol ratio)=0.0114.
Claims (5)
1. a preparation method for heteroatoms MCM-49 zeolite molecular sieve, its concrete steps are as follows:
A, by mixture heating hydrolysis in acidic medium in silicon source and heteroatoms source, controlling the pH value of solution is 1.0-6.0, obtains solution A; Wherein said heteroatoms source is containing the one in the oxide compound of Fe, V, Co, Cr, Ni, Mn, Ga or Zr element, muriate, nitrate, vitriol and acetate;
B, aluminium source and inorganic alkali source spent ionized water and dissolve, obtain solution B;
C, be added drop-wise in solution A by solution B, the mol ratio that mixture is always formed is: SiO
2/ Al
2o
3=20-100, M
2o/SiO
2=0.1-0.3, Me/SiO
2=0.0025-0.05, H
2o/SiO
2=15-50, wherein M is monovalent base metal ion, and Me is heteroatom elements;
D, above-mentioned reaction mixture heat drying is obtained dry glue;
E, above-mentioned dry glue is placed in reactor upper gaseous phase position, template hexamethylene imine (HMI) and water are placed in reactor lower liquid phase position according to the mixture that mass ratio 0.05-0.2: 1 forms, sealing, be warmed up to crystallization temperature, by solid product washing, centrifugal, dry, roasting after crystallization terminates, obtain skeleton containing heteroatomic MCM-49 zeolite molecular sieve.
2. synthetic method according to claim 1, is characterized in that described silicon source is silicate, silicon sol, silicon-dioxide, tetraethoxy or methyl silicate.
3. synthetic method according to claim 1, is characterized in that described acidic medium is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrofluoric acid or careless aqueous acid.
4. synthetic method according to claim 1, is characterized in that described aluminium source is Tai-Ace S 150, aluminum chloride, sodium aluminate, aluminum nitrate, aluminum isopropylate, pseudo-boehmite or aluminium powder; Inorganic alkali source is sodium hydroxide or potassium hydroxide.
5. synthetic method according to claim 1, it is characterized in that the hydrolysis temperature described in step a is 20-90 DEG C, hydrolysis time is 2-24 hour; Drying temperature described in steps d is 50-100 DEG C, and time of drying is 2-24 hour; Crystallization temperature described in step e is 140-180 DEG C, and crystallization time is 3-15 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410740431.1A CN104445255A (en) | 2014-12-04 | 2014-12-04 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410740431.1A CN104445255A (en) | 2014-12-04 | 2014-12-04 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104445255A true CN104445255A (en) | 2015-03-25 |
Family
ID=52892119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410740431.1A Pending CN104445255A (en) | 2014-12-04 | 2014-12-04 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104445255A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083509A (en) * | 2016-06-20 | 2016-11-09 | 中国石油大学(北京) | The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins |
| CN109174172A (en) * | 2018-11-07 | 2019-01-11 | 南京大学连云港高新技术研究院 | A kind of preparation method of the low temperature catalyst for SCR reaction |
| CN109437226A (en) * | 2018-11-01 | 2019-03-08 | 山东国瓷功能材料股份有限公司 | A kind of Cu-SSZ-13 molecular sieve and preparation method thereof |
| CN109939726A (en) * | 2019-04-08 | 2019-06-28 | 中国科学院山西煤炭化学研究所 | A kind of preparation and application of the catalyst of the molecular sieve of MTT containing hetero atom |
| CN114933315A (en) * | 2022-06-06 | 2022-08-23 | 中海油天津化工研究设计院有限公司 | High hydrothermal stability UZM-8 molecular sieve and preparation method thereof |
| CN115106120A (en) * | 2022-06-14 | 2022-09-27 | 天津大学 | Dehydrogenation catalyst, preparation method and application thereof |
| CN117142486A (en) * | 2023-08-31 | 2023-12-01 | 中国石油大学(北京) | MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051334A (en) * | 1989-10-28 | 1991-05-15 | 太原工业大学 | The method of synthesis of zeolite by vapor phase |
| CN1639065A (en) * | 2002-03-07 | 2005-07-13 | 昭和电工株式会社 | MWW type zeolite substance, precursor substance therefor, and process for producing these substances |
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN102009985A (en) * | 2010-12-21 | 2011-04-13 | 南京工业大学 | MCM-22 zeolite molecular sieve with framework containing rare earth heteroatoms and preparation method thereof |
| CN102464340A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing silicoaluminophosphate (SAPO)-34 molecular sieve |
| CN102674388A (en) * | 2012-06-06 | 2012-09-19 | 北京化工大学 | Method for preparing zeolite molecular sieve catalyst through circulating gas phase method |
-
2014
- 2014-12-04 CN CN201410740431.1A patent/CN104445255A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051334A (en) * | 1989-10-28 | 1991-05-15 | 太原工业大学 | The method of synthesis of zeolite by vapor phase |
| CN1639065A (en) * | 2002-03-07 | 2005-07-13 | 昭和电工株式会社 | MWW type zeolite substance, precursor substance therefor, and process for producing these substances |
| CN101993095A (en) * | 2010-10-28 | 2011-03-30 | 神华集团有限责任公司 | Method for preparing SAPO-5 molecular sieve and product obtained through same |
| CN102464340A (en) * | 2010-11-17 | 2012-05-23 | 中国石油化工股份有限公司 | Method for synthesizing silicoaluminophosphate (SAPO)-34 molecular sieve |
| CN102009985A (en) * | 2010-12-21 | 2011-04-13 | 南京工业大学 | MCM-22 zeolite molecular sieve with framework containing rare earth heteroatoms and preparation method thereof |
| CN102674388A (en) * | 2012-06-06 | 2012-09-19 | 北京化工大学 | Method for preparing zeolite molecular sieve catalyst through circulating gas phase method |
Non-Patent Citations (2)
| Title |
|---|
| 刘中清等: "含Zn MWW结构分子筛的合成", 《石油学报(石油加工)》 * |
| 刘星生等: "硅铝胶气相法合成MCM-22分子筛工艺条件的影响", 《化学反应工程与工艺》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083509A (en) * | 2016-06-20 | 2016-11-09 | 中国石油大学(北京) | The method of crome metal skeleton doped molecular sieve catalytic pyrolysis normal butane producing light olefins |
| CN109437226A (en) * | 2018-11-01 | 2019-03-08 | 山东国瓷功能材料股份有限公司 | A kind of Cu-SSZ-13 molecular sieve and preparation method thereof |
| CN109437226B (en) * | 2018-11-01 | 2022-03-11 | 山东国瓷功能材料股份有限公司 | Cu-SSZ-13 molecular sieve and preparation method thereof |
| CN109174172A (en) * | 2018-11-07 | 2019-01-11 | 南京大学连云港高新技术研究院 | A kind of preparation method of the low temperature catalyst for SCR reaction |
| CN109939726A (en) * | 2019-04-08 | 2019-06-28 | 中国科学院山西煤炭化学研究所 | A kind of preparation and application of the catalyst of the molecular sieve of MTT containing hetero atom |
| CN114933315A (en) * | 2022-06-06 | 2022-08-23 | 中海油天津化工研究设计院有限公司 | High hydrothermal stability UZM-8 molecular sieve and preparation method thereof |
| CN115106120A (en) * | 2022-06-14 | 2022-09-27 | 天津大学 | Dehydrogenation catalyst, preparation method and application thereof |
| CN115106120B (en) * | 2022-06-14 | 2024-01-19 | 天津大学 | Dehydrogenation catalyst, preparation method and application thereof |
| CN117142486A (en) * | 2023-08-31 | 2023-12-01 | 中国石油大学(北京) | MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural |
| CN117142486B (en) * | 2023-08-31 | 2024-05-10 | 中国石油大学(北京) | MWW structure molecular sieve, preparation method thereof and application thereof in preparation of 5-hydroxymethylfurfural |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104445255A (en) | Preparation method of heteroatom MCM-49 zeolite molecular sieve | |
| CN102627287B (en) | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials | |
| CN102923730B (en) | Titanium-silicon molecular sieve, preparation method thereof and method for preparing cyclohexanone oxime by using molecular sieve | |
| CN102502687B (en) | Method for greenly synthesizing Ti-Si molecular sieve | |
| CN101717095B (en) | Synthesizing method of small-crystal particle rare earth-ZSM5/ZSM11 co-crystallizing zeolite | |
| CN105347359B (en) | A kind of duct includes the synthesis and its application of the zeolite molecular sieve of solid acid | |
| CN102009985B (en) | MCM-22 zeolite molecular sieve with framework containing rare earth heteroatoms and preparation method thereof | |
| CN105728019A (en) | Application and preparation method of ZSM-5 molecular sieve with mesopores and micropores | |
| CN109311687A (en) | The method of continuous synthetic zeolite material | |
| CN104098110B (en) | Preparation method and application of B-Al-ZSM-5 zeolite with controllable particle diameter | |
| CN103232044A (en) | Synthesis method of nanoscale MCM-49 (Multi Chip Module) molecular sieve | |
| CN110342535A (en) | A kind of preparation method for the porous HZSM-5 zeolite molecular sieve that soda acid is modified | |
| US10287172B2 (en) | Preparation method for beta zeolite | |
| CN104386707B (en) | A kind of synthetic method of super low-Na and high-Si nano-ZSM-5 molecular sieve | |
| CN105197955A (en) | Method for low-temperature solvent-free synthesis of high-silicon small-size Cu-SSZ-13 zeolite molecular sieve | |
| CN103447069A (en) | Catalytic cracking catalyst containing Y-type molecular sieve and preparation method thereof | |
| CN106082262A (en) | The preparation method of Hydrogen ZSM 11 molecular sieve | |
| CN102897788B (en) | Synthesis method for ZSM-11 molecular sieve | |
| CN104556105B (en) | Aerosol-assisted synthesis method of Beta molecular sieve | |
| CN103723741A (en) | Method for synthesizing ZSM-5/MCM-41 composite molecular sieve | |
| CN105858680A (en) | Method for directly synthesizing Cu-doped zeolite CHA by taking cheap Si and Al as raw materials | |
| CN103204505B (en) | Preparation method of aluminum-containing layered kenyaite | |
| CN114669325B (en) | Preparation method and application of supported TS-1 catalyst | |
| CN105084388B (en) | Method for preparing and modifying Y-type molecular sieve | |
| CN105621433B (en) | A kind of preparation method for having core shell structure Y Beta composite molecular screens |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150325 |