CN102009985B - MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof - Google Patents
MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof Download PDFInfo
- Publication number
- CN102009985B CN102009985B CN2010105984615A CN201010598461A CN102009985B CN 102009985 B CN102009985 B CN 102009985B CN 2010105984615 A CN2010105984615 A CN 2010105984615A CN 201010598461 A CN201010598461 A CN 201010598461A CN 102009985 B CN102009985 B CN 102009985B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- mcm
- zeolite molecular
- rare
- solution
- 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.)
- Expired - Fee Related
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 88
- 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 88
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 66
- 239000010457 zeolite Substances 0.000 title claims abstract description 66
- 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 65
- 150000002910 rare earth metals Chemical group 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 29
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013078 crystal Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 230000003068 static effect Effects 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 60
- 230000007062 hydrolysis Effects 0.000 claims description 26
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 22
- -1 rare earth compound Chemical class 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-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
- 229910052772 Samarium Inorganic materials 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229960001866 silicon dioxide Drugs 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 4
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 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
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 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
- 239000000047 product Substances 0.000 abstract description 37
- 238000003756 stirring Methods 0.000 abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000009616 inductively coupled plasma Methods 0.000 description 32
- 238000002441 X-ray diffraction Methods 0.000 description 25
- 239000002253 acid Substances 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZBGLGVFYHCSILI-UHFFFAOYSA-N acetic acid;europium Chemical compound [Eu].CC(O)=O ZBGLGVFYHCSILI-UHFFFAOYSA-N 0.000 description 1
- DGVVPRHPLWDELQ-UHFFFAOYSA-N acetic acid;samarium Chemical compound [Sm].CC(O)=O.CC(O)=O.CC(O)=O DGVVPRHPLWDELQ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an MCM-22 zeolite molecular sieve containing rare earth heteroatoms in a skeleton and a hydrothermal synthesis method thereof. The method is characterized by comprising the following steps: regulating the pH value of the mixed solution of a silicon source and a rear earth source to perform co-hydrolysis and obtain a silicone gel precursor containing rear earth; then adding an organic template agent to obtain a solution A; mixing water, an aluminum source and an alkali source uniformly according to a certain proportion to obtain a solution B; slowly adding the solution B in the solution A dropwise to obtain a crystallization liquid; and placing the crystallization liquid in a hydrothermal kettle, sealing and performing the static hydrothermal crystallation for 5-30 days at 140-180 DEG C to obtain the skeleton rare-earth heteroatom molecular sieve MCM-22 with the MCM-22 crystal structure. The method avoids the phenomenon that only rare-earth heteroatoms are hydrolyzed to generate oxide precipitate; the crystallization process uses the static method without the stirring step, thereby simplifying the operating condition and reducing the production difficulty. In addition, the product has high crystallization degree and high hydrothermal stability and the preparation method has good repeatability.
Description
Technical field
The present invention relates to a kind of skeleton and contain MCM-22 hetero-atom molecular-sieve of rare earth and preparation method thereof.More particularly, zeolite molecular sieve provided by the invention has the crystal structure characteristic of MCM-22, and contains REE on the zeolite molecular sieve crystal skeleton structure.
Background technology
Zeolite MCM-22 was first developed by the United States out of Mobil Corporation MWW topology having a zeolite molecular sieve material (US4954325), which has two separate, mutually communicating channel system (Science, 1994,264:1910 - 1912): First, a pore size of
$ 10 ring-dimensional sinusoidal channels; Second, through
10-membered ring openings communicating with the outside diameter of
$ 12 supercages.The MCM-22 molecular sieve is with its unique pore structure, good heat/hydrothermal stability and proper acidic; In isomerizing, disproportionation, catalytic cracking processes such as (US4983276), be widely used gradually; Alkylation (US4992606 at benzene and propylene, ethene; US4992615 US5334795) has been used as commercial catalysts in the technology, have wide practical use.
As everyone knows, REE is introduced the hydrothermal stability that zeolite molecular sieve can improve zeolite molecular sieve, suppress zeolite continuation dealuminzation in use, strengthen catalyst activity, improve the anti-metallic pollution performance of catalyzer.Mainly be REE to be scattered in zeolite molecular sieve surface or the duct at present through dipping (US4900428), vapour deposition (US437429, CN8607531, CN1034680A) and IX methods such as (US4178269, US4152362).But because the hydrated ion diameter of rare earth is 7.9 * 10
-10M, and the linear channel diameter of MCM-22 molecular sieve is 4.0 * 5.9 * 10
-10M; Thereby be difficult in the MCM-22 molecular sieve, introduce rare earth ion with conventional ion-exchange techniques; The silica alumina ratio of MCM-22 molecular sieve is very high in addition, the cation-bit that can be used for IX seldom, so the rare earth ion exchanged method is not effective ways concerning MCM-22; Adopt dipping or vapour deposition process that REE is loaded to shortcomings such as then having metallic element skewness, the easy loss of active ingredient on the molecular sieve, seriously hindered the further raising of rare earth containing zeolite catalyzer hydrothermal stability and catalytic activity.
In order to improve these defectives; Can in zeolite molecular sieve is synthetic, add the salt that contains REE; Make REE in the zeolite crystallization process, get into framework of molecular sieve, so just might make the high rare earth zeolite catalyst of dispersity, and the possibility that can avoid the REE in the skeleton under hydrogen atmosphere, to be reduced to metal and to volatilize and run off; Can effectively improve catalyst stability; The more important thing is that the skeleton rare earth can be stablized skeleton structure of zeolite, improve heat and the hydrothermal stability of zeolite in the catalytic applications process.But rare earth ion in the normally used alkaline medium of zeolite water thermal synthesis very easily hydrolysis generate indissoluble oxyhydroxide or oxide precipitation; Stop REE effectively to get into framework of molecular sieve, therefore must adopt novel synthesis path just might REE be incorporated in the zeolite molecular sieve skeleton.
Be to explore the approach of in zeolite molecular sieve, introducing REE, patent CN1058382A adopts xenocryst guiding method in synthesizing five-membered ring structure high-silicon zeolite system, to add rare earth X or rare earth exchanged Y zeolite is a crystal seed, and hydro-thermal is synthesized and obtained a kind of ZSM-5 zeolite that contains rare earth.CN1147420A has further improved compound method, obtains having the phosphorous molecular sieve with rare earth of MFI structure, and this molecular sieve has good hydrothermal stability.CN1209356A also adopts xenocryst guiding method to synthesize beta zeolite containing rare earth, and this zeolite molecular sieve has high anti-nitrogen ability and high stability.But because xenocryst guiding method has been introduced foreign crystal in the zeolite molecular sieve building-up process, it is impure to make crystallization process generate the crystal or the synthetic zeolite molecular sieve of other non-title product easily; And use the synthetic cost of crystal seed introducing REE higher.In addition, the relevant report that adopts other method synthesizing rare-earth zeolite molecular sieve is also arranged.Wang Xiaohan etc. (petroleum journal (refining of petroleum), 1994, with the n-Butyl Amine 99 template 10:61-67), in synthetic system, add crystal seed, hydrothermal crystallizing has obtained the La-Al-ZSM-5 molecular sieve.(petroleum journal (refining of petroleum) such as Wang Xiangsheng; 1996; 12:17-23) respectively with 1,6-hexanediamine and tetraethyl ammonium hydroxide are template, have synthesized series of rare earth zeolite molecular sieves such as La-ZSM-5, La-ZSM-48, La-ZSM-12, Ce-β, Ce-ZSM-12, Ce-ZSM-5.Mohamed etc. (Microporous and Mesoporous Materials, 2006, be that template has been synthesized the Ce-Mordenite zeolite molecular sieve with the O-Phenylene Diamine 93:71-81).Xie Sujuan etc. (CN101468800A) are that double template has synthesized the MCM-49 molecular sieve that contains rare earth with hexamethylene imine and hexahydroaniline.Though the MCM-22 zeolite molecular sieve has demonstrated important industrial application value, there is not skeleton to contain any patent and the bibliographical information of the MCM-22 structural zeolite molecular sieve of REE at present.
Summary of the invention
The purpose of this invention is to provide the MCM-22 zeolite molecular sieve that a kind of skeleton contains rare-earth heteroatoms, another object of the present invention has provided the preparation method that above-mentioned skeleton contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms.
Technical scheme of the present invention is: in building-up process, generate oxyhydroxide or hydrous oxide deposition in order to reduce rare-earth heteroatoms effectively because of hydrolysis; Help rare-earth heteroatoms and get into framework of molecular sieve; The present invention adopts silicon source and rare earth compound cohydrolysis in acidic medium to prepare rare earth silicate colloidal sol precursor; Rare-earth heteroatoms RE is existed with the form of Si-O-RE, and then above-mentioned precursor hydrothermal crystallizing under alkaline condition is obtained skeleton rare-earth heteroatoms zeolite molecular sieve.Rare-earth heteroatoms wherein gets into the skeleton of zeolite molecular sieve crystal through X-ray diffraction and IR spectroscopy proof.
Technical solution of the present invention is: a kind of skeleton contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms; It is characterized in that: contain REE in the skeleton of this zeolite molecular sieve crystal, wherein said REE is one or both in lanthanum, cerium, praseodymium, neodymium, samarium or the europium; REE is 0.001-0.03 with the mol ratio of silicon in the skeleton of zeolite molecular sieve crystal.
The present invention also provides preparing method's method of the MCM-22 zeolite molecular sieve that above-mentioned skeleton contains rare-earth heteroatoms, and its concrete steps are following:
A kind of method for preparing rare-earth heteroatoms zeolite molecular sieve as claimed in claim 1, its concrete steps are following:
A, with mixture heating hydrolysis in acidic medium of silicon source and rare earth compound, the pH value of control solution is 1.0 ~ 6.0, in above-mentioned hydrolysate, adds template then, obtains solution A;
B, aluminium source and inorganic alkali source are spent the ionized water dissolving, obtain solution B;
C, solution B is added drop-wise in the solution A, makes the total mol ratio of forming of mixture be: SiO
2/ Al
2O
3=20-100, M
2O/SiO
2=0.1-0.3, HMI/SiO
2=0.1-1.0, RE/SiO
2=0.0025-0.05, H
2O/SiO
2=10-50, wherein M is the monovalent base metals ion, HMI is the template hexamethylene imine; RE is a REE;
D, above-mentioned reaction mixture is packed in the water heating kettle, sealing is warmed up to crystallization temperature, and static crystallization under autogenous pressure with solid product washing, centrifugal, dry, roasting, obtains the MCM-22 zeolite molecular sieve that skeleton contains rare-earth heteroatoms then.
Preferred above-mentioned silicon source is silicate, silicon sol, silicon-dioxide, tetraethoxy or methyl silicate.
Preferred above-mentioned rare earth compound is one or both the mixture in nitrate salt, muriate, vitriol and the acetate that contains rare earth.
Preferred said acidic medium is the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrofluoric acid or oxalic acid.
Preferred 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 Pottasium Hydroxide.
Above-mentioned raw materials market is on sale.
Hydrolysis temperature described in the preferred steps a is 20 ~ 90 ° of C, and hydrolysis time is 2 ~ 24 hours; Crystallization temperature described in the steps d is 140 ~ 180 ° of C, and crystallization time is 5 ~ 30 days.Normal condition is pressed in washing, centrifugal, dry, roasting.
Beneficial effect:
(1) adopt the amorphous thing to introduce REE, synthetic cost is low, and the zeolite product purity is high, good reproducibility, and the content of rare earth of prepared rare earth MCM-22 molecular sieve is adjustable.
(2) crystallization process adopts stationary method, does not need to stir, and has simplified operational condition, has reduced the production difficulty.
(3) prepared rare earth MCM-22 molecular sieve has good hydrothermal stability.800 ° of samples that the C/100% water vapor conditions wore out 4 hours down still keep good MCM-22 crystal structure of molecular sieve characteristic.
Description of drawings
Fig. 1 a, b, c and d are respectively the X-ray diffractograms of Comparative Examples 1, embodiment 1,2 and 3 gained sieve samples;
Fig. 2 a, b and c are respectively the infrared spectrograms of Comparative Examples 1, embodiment 1 and 2 gained sieve samples.
Embodiment
Below in conjunction with embodiment the present invention is done further explanation, but therefore do not limit the present invention.
Comparative Examples 1
Get tetraethoxy 11.31g, to the 0.3M aqueous hydrochloric acid that wherein adds 10.25ml, the hydrolysis pH value to 2.0 of regulator solution stirs hydrolysis 2 hours in 90 ° of C, adds the 3.44ml hexamethylene imine again, processes A solution; 0.315g sodium hydroxide and 0.415g sodium aluminate solution are processed B solution in the 8.4ml deionized water, solution B is added drop-wise in the solution A at leisure, stir, make that the total mol ratio of forming of mixture is SiO
2: 0.125Na
2O:0.033Al
2O
3: 0.6HMI:20H
2O is encapsulated into high-pressure hydrothermal reaction kettle, and crystallization is 6 days under 158 ° of C, with not contained heteroatomic MCM-22 molecular screen primary powder after products therefrom washing to neutral, centrifugal, dry, the roasting.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 a, and infrared spectrum (IR) is seen Fig. 2 a.
Embodiment 1
Get tetraethoxy 11.31g, Lanthanum trinitrate 0.231g, to the 0.3M aqueous hydrochloric acid that wherein adds 10.25ml, the hydrolysis pH value to 2.0 of regulator solution stirs hydrolysis 2 hours in 90 ° of C, adds the 3.44ml hexamethylene imine again, processes A solution; 0.315g sodium hydroxide and 0.415g sodium aluminate solution are processed B solution in the 8.4ml deionized water, solution B is added drop-wise in the solution A at leisure, stir, make that the total mol ratio of forming of mixture is SiO
2: 0.125Na
2O:0.033Al
2O
3: 0.01RE:0.6HMI:20H
2O; Be encapsulated into high-pressure hydrothermal reaction kettle; Crystallization is 10 days under 158 ° of C, and to neutral, centrifugal, dry, roasting, product proves through X-ray diffraction, infrared spectrum characterization result: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum with the products therefrom washing.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 b, and infrared spectrum (IR) is seen Fig. 2 b.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0068 in the molecular sieve.
Embodiment 2
According to operation steps and the operational condition of embodiment 1, difference is that rare earth compound is a cerous nitrate, and product proves through X-ray diffraction, infrared spectrum characterization result: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of cerium.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 c, and infrared spectrum (IR) is seen Fig. 2 c.Adopt inductively coupled plasma spectrography (ICP) to record the Ce/Si (mol ratio)=0.0083 in the molecular sieve.
Embodiment 3
According to operation steps and the operational condition of embodiment 1, difference is that rare earth compound is a samaric nitrate, and product characterizes proof through the XRD diffraction: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of samarium.Its X-ray diffraction spectrogram (XRD) is seen Fig. 1 d.Adopt inductively coupled plasma spectrography (ICP) to record the Sm/Si (mol ratio)=0.0060 in the molecular sieve.
Embodiment 4
According to operation steps and the operational condition of embodiment 1, difference is that rare earth compound is the mixture of lanthanum sulfat and cerous sulfate, and products therefrom characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum and samarium.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0029 in the molecular sieve, Ce/Si (mol ratio)=0.0033.
Embodiment 5
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a methyl silicate, and rare earth compound is a praseodymium sulfate, and acid solution is a sulfuric acid, and the total mol ratio of forming of mixture is SiO
2: 0.2Na
2O:0.01Al
2O
3: 0.005RE:0.6HMI:30H
2O, crystallization temperature are 158 ° of C, and crystallization time is 20 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of praseodymium.Adopt inductively coupled plasma spectrography (ICP) to record the Pr/Si (mol ratio)=0.0030 in the molecular sieve.
Embodiment 6
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a methyl silicate, and rare earth compound is a Neodymium trichloride, and crystallization temperature is 158 ° of C, and crystallization time is 30 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of neodymium.Adopt inductively coupled plasma spectrography (ICP) to record the Nd/Si (mol ratio)=0.0071 in the molecular sieve.
Embodiment 7
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a methyl silicate, and rare earth compound is the acetic acid europium, and acid solution is an acetic acid, and crystallization temperature is 158 ° of C, and crystallization time is 30 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of europium.Adopt inductively coupled plasma spectrography (ICP) to record the Eu/Si (mol ratio)=0.0066 in the molecular sieve.
Embodiment 8
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon sol, and rare earth compound is a Lanthanum trichloride, and the aluminium source is an aluminum chloride, and acid solution is a nitric acid, and hydrolysis pH value is 1.0, and the total mol ratio of forming of mixture is SiO
2: 0.3Na
2O:0.02Al
2O
3: 0.05RE:1.0HMI:50H
2O, crystallization temperature are 178 ° of C, and crystallization time is 30 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.028 in the molecular sieve.
Embodiment 9
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon sol, and rare earth compound is a cerous nitrate, and the aluminium source is an aluminum nitrate, and alkali source is a Pottasium Hydroxide, and hydrolysis pH value is 4.0, and acid solution is a phosphoric acid, and the total mol ratio of forming of mixture is SiO
2: 0.15K
2O:0.05Al
2O
3: 0.005RE:0.6HMI:20H
2O, crystallization temperature are 168 ° of C, and crystallization time is 20 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of cerium.Adopt inductively coupled plasma spectrography (ICP) to record the Ce/Si (mol ratio)=0.0032 in the molecular sieve.
Embodiment 10
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon sol, and the aluminium source is an aluminum isopropylate; Rare earth compound is the acetic acid samarium, and acid solution is a hydrofluoric acid, and hydrolysis pH value is 3.0; 20 ° of C stir hydrolysis 24 hours, and the total mol ratio of forming of mixture is SiO
2: 0.25Na
2O:0.01Al
2O
3: 0.0025RE:1.0HMI:10H
2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of samarium.Adopt inductively coupled plasma spectrography (ICP) to record the Sm/Si (mol ratio)=0.0013 in the molecular sieve.
Embodiment 11
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a water glass, and the aluminium source is an aluminum chloride, and rare earth compound is a lanthanum acetate, and acid solution is an acetic acid, and the total mol ratio of forming of mixture is SiO
2: 0.15Na
2O:0.033Al
2O
3: 0.0025RE:0.1HMI:20H
2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0015 in the molecular sieve.
Embodiment 12
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a water glass, and the aluminium source is a Tai-Ace S 150; Rare earth compound is a cerous sulfate; Inorganic alkali source is a Pottasium Hydroxide, and acid solution is a sulfuric acid, and hydrolysis pH value is 4.0; 20 ° of C stir hydrolysis 24 hours, and the total mol ratio of forming of mixture is SiO
2: 0.15K
2O:0.033Al
2O
3: 0.0025RE:0.6HMI:35H
2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of cerium.Adopt inductively coupled plasma spectrography (ICP) to record the Ce/Si (mol ratio)=0.0014 in the molecular sieve.
Embodiment 13
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a water glass, and the aluminium source is an aluminum nitrate; Rare earth compound is a samarium trichloride, and acid solution is a nitric acid, and hydrolysis pH value is 5.0; 40 ° of C stir hydrolysis 12 hours, and the total mol ratio of forming of mixture is SiO
2: 0.2Na
2O:0.033Al
2O
3: 0.01RE:0.6HMI:35H
2O, crystallization temperature are 140 ° of C, and crystallization time is 20 days.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of samarium.Adopt inductively coupled plasma spectrography (ICP) to record the Sm/Si (mol ratio)=0.0073 in the molecular sieve.
Embodiment 14
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon-dioxide, and the aluminium source is a Tai-Ace S 150, and hydrolysis pH value is that 6.0,60 ° of C stir hydrolysis 8 hours, and the total mol ratio of forming of mixture is SiO
2: 0.2Na
2O:0.033Al
2O
3: 0.01RE:0.6HMI:35H
2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0075 in the molecular sieve.
Embodiment 15
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon-dioxide, and the aluminium source is a pseudo-boehmite, and hydrolysis pH value is that 6.0,60 ° of C stir hydrolysis 8 hours, and the total mol ratio of forming of mixture is SiO
2: 0.2Na
2O:0.02Al
2O
3: 0.01RE:0.6HMI:35H
2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of lanthanum.Adopt inductively coupled plasma spectrography (ICP) to record the La/Si (mol ratio)=0.0072 in the molecular sieve.
Embodiment 16
According to operation steps and the operational condition of embodiment 1, difference is that the silicon source is a silicon-dioxide, and the aluminium source is an aluminium powder, and rare earth compound is a Neodymium trichloride, and hydrolysis pH value is that 6.0,90 ° of C stir hydrolysis 4 hours, and the total mol ratio of forming of mixture is SiO
2: 0.2Na
2O:0.033Al
2O
3: 0.01RE:0.6HMI:40H
2O.Product characterizes proof through XRD: its product that finally obtains is the adulterated MCM-22 zeolite molecular sieve of neodymium.Adopt inductively coupled plasma spectrography (ICP) to record the Nd/Si (mol ratio)=0.0069 in the molecular sieve.
With the rare earth MCM-22 molecular sieve of above-mentioned preparation aging 4 hours sample under 800 ° of C/100% water vapor conditions, still keep good MCM-22 crystal structure of molecular sieve characteristic; Has good hydrothermal stability.
Claims (5)
1. a skeleton contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that: contain in lanthanum, cerium, praseodymium, neodymium, samarium or the europium REE one or both in the skeleton of this zeolite molecular sieve crystal; Wherein REE is 0.001-0.03 with the mol ratio of silicon in the zeolite molecular sieve crystal skeleton; Made by following method, its concrete steps are following:
A, with mixture heating hydrolysis in acidic medium of silicon source and rare earth compound, the pH value of control solution is 1.0 ~ 6.0, in above-mentioned hydrolysate, adds template then, obtains solution A; Wherein said rare earth compound is one or both the mixture in nitrate salt, muriate, vitriol and the acetate that contains rare earth;
B, aluminium source and inorganic alkali source are spent the ionized water dissolving, obtain solution B;
C, solution B is added drop-wise in the solution A, makes the total mol ratio of forming of mixture be: SiO
2/ Al
2O
3=20-100, M
2O/SiO
2=0.1-0.3, HMI/SiO
2=0.1-1.0, RE/SiO
2=0.0025-0.05, H
2O/SiO
2=10-50, wherein M is the monovalent base metals ion, HMI is the template hexamethylene imine; RE is a REE;
D, above-mentioned reaction mixture is packed in the water heating kettle, sealing is warmed up to crystallization temperature, and static crystallization with solid product washing, centrifugal, dry, roasting, obtains the MCM-22 zeolite molecular sieve that skeleton contains rare-earth heteroatoms then.
2. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that described silicon source is silicate, silicon sol, silicon-dioxide, tetraethoxy or methyl silicate.
3. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that said acidic medium is the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrofluoric acid or oxalic acid.
4. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it 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 Pottasium Hydroxide.
5. skeleton according to claim 1 contains the MCM-22 zeolite molecular sieve of rare-earth heteroatoms, it is characterized in that the hydrolysis temperature described in the step a is 20 ~ 90 ° of C, and hydrolysis time is 2 ~ 24 hours; Crystallization temperature described in the steps d is 140 ~ 180 ° of C, and crystallization time is 5 ~ 30 days.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010105984615A CN102009985B (en) | 2010-12-21 | 2010-12-21 | MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN2010105984615A CN102009985B (en) | 2010-12-21 | 2010-12-21 | MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN102009985A CN102009985A (en) | 2011-04-13 |
CN102009985B true CN102009985B (en) | 2012-11-21 |
Family
ID=43840345
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN2010105984615A Expired - Fee Related CN102009985B (en) | 2010-12-21 | 2010-12-21 | MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN102009985B (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102351211B (en) * | 2011-08-01 | 2012-11-21 | 大连理工大学 | Synthesis method of MCM-22 family molecular sieve |
JP6232058B2 (en) | 2012-06-27 | 2017-11-15 | 中国石油化工股▲ふん▼有限公司 | Catalytic cracking catalyst containing modified Y-type zeolite and process for its preparation |
CN103657700B (en) * | 2012-09-14 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
CN103657701B (en) * | 2012-09-14 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
CN103848433B (en) * | 2012-11-30 | 2016-03-09 | 中国石油天然气股份有限公司 | A kind of method of producing MCM-49 molecular sieve |
CN103204519B (en) * | 2013-04-15 | 2015-06-03 | 珠海市吉昌稀土有限公司 | Synthetic method of rare-earth silicon-aluminum molecular sieve |
CN104402021A (en) * | 2014-11-04 | 2015-03-11 | 南京工业大学 | Preparation method of MCM-49 zeolite molecular sieve |
CN104445255A (en) * | 2014-12-04 | 2015-03-25 | 南京工业大学 | Preparation method of heteroatom MCM-49 zeolite molecular sieve |
CN106890675B (en) * | 2015-12-18 | 2020-02-14 | 中国石油天然气股份有限公司 | Preparation method of rare earth-containing catalytic cracking catalyst |
WO2017210812A1 (en) * | 2016-06-06 | 2017-12-14 | Rhodia Operations | Rare earth zeolite and the method of preparation thereof |
CN109201110B (en) * | 2017-07-06 | 2021-07-23 | 中国科学院上海高等研究院 | Rare earth element modified hydroisomerization catalyst and synthesis method and application thereof |
CN107500308B (en) * | 2017-08-15 | 2020-06-02 | 上海交通大学 | Preparation method of rare earth modified hierarchical pore titanium silicalite molecular sieve |
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 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1789126A (en) * | 2004-12-17 | 2006-06-21 | 中国科学院大连化学物理研究所 | Synthetic method for MCM-22 molecular sieve |
CN101618336A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Metal supported MCM-22 molecular sieve hollow sphere bifunctional catalyst preparation method and application thereof |
-
2010
- 2010-12-21 CN CN2010105984615A patent/CN102009985B/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1789126A (en) * | 2004-12-17 | 2006-06-21 | 中国科学院大连化学物理研究所 | Synthetic method for MCM-22 molecular sieve |
CN101618336A (en) * | 2009-08-03 | 2010-01-06 | 大连理工大学 | Metal supported MCM-22 molecular sieve hollow sphere bifunctional catalyst preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN102009985A (en) | 2011-04-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102009985B (en) | MCM-22 zeolite molecular sieve containing rare earth heteroatoms in skeleton and preparation method thereof | |
CN102627287B (en) | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials | |
CN1321061C (en) | Method of synthesizing Ti-MWW molecular sieve | |
CN101353168B (en) | Synthetic method of nano aluminum-rich beta-zeolite | |
WO2019022782A1 (en) | Methods for producing hierarchical mesoporous zeolite beta | |
CN101405220A (en) | A process for preparing nano size zeolites | |
CN101679055A (en) | Novel process for preparing zeolite eu-1 | |
CN104445255A (en) | Preparation method of heteroatom MCM-49 zeolite molecular sieve | |
CN103747849A (en) | Reduction of oxides of nitrogen in a gas stream using molecular sieve SSZ-23 | |
CN100475698C (en) | Im-10 type crystalline solid and process for preparation | |
CN1035668C (en) | Method No.1 for synthesizing beta zealite | |
CN110193379A (en) | A kind of preparation method and applications of CuRE/SAPO-34 molecular sieve | |
TW200404744A (en) | Process for the preparation of doped pentasil-type zeolites using a doped reactant | |
CN106673001A (en) | Synthesis method of ZSM-11 molecular sieve and ZSM-11 molecular sieve synthesized through same | |
CN101863492A (en) | Synthesis method of 4A-type zeolite | |
CN106673000B (en) | The synthetic method of ZSM-11 molecular sieves containing rare earth metal and its molecular sieve of synthesis | |
CN105084388B (en) | Method for preparing and modifying Y-type molecular sieve | |
CN1353087A (en) | Process for preparing ZSM-5 molecular sieve | |
CN112551544B (en) | Method for producing IZM-2 zeolites in the presence of a nitrogen-containing organic structuring agent in the hydroxide form in an optionally fluorinated medium | |
CN105621433B (en) | A kind of preparation method for having core shell structure Y Beta composite molecular screens | |
CN112551543B (en) | Method for preparing IZM-2 zeolite in the presence of mixture of nitrogen-containing organic structuring agent in hydroxide and bromide form | |
JPH0940417A (en) | Production of crystalline microporous substance | |
CN102009984B (en) | Method for preparing molecular sieve from chlorosilane | |
CN100594179C (en) | Micropore crystalline aluminium silicate and its preparation process | |
CN100363258C (en) | Method for preparing silicon-aluminum molecular sieve in EUO structure |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20121121 Termination date: 20151221 |
|
EXPY | Termination of patent right or utility model |