CN113860327B - ERI type magnesium-silicon-aluminum molecular sieve, synthesis method and application thereof - Google Patents
ERI type magnesium-silicon-aluminum molecular sieve, synthesis method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 118
- 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 118
- -1 magnesium-silicon-aluminum Chemical compound 0.000 title claims abstract description 23
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- MKPXGEVFQSIKGE-UHFFFAOYSA-N [Mg].[Si] Chemical compound [Mg].[Si] MKPXGEVFQSIKGE-UHFFFAOYSA-N 0.000 claims abstract description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000003463 adsorbent Substances 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 23
- 239000000395 magnesium oxide Substances 0.000 claims description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 22
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 10
- 239000000347 magnesium hydroxide Substances 0.000 claims description 10
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- WUPZNKGVDMHMBS-UHFFFAOYSA-N azane;dihydrate Chemical compound [NH4+].[NH4+].[OH-].[OH-] WUPZNKGVDMHMBS-UHFFFAOYSA-N 0.000 claims description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000004645 aluminates Chemical class 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims 6
- 239000011541 reaction mixture Substances 0.000 claims 3
- 239000008236 heating water Substances 0.000 claims 2
- 229910000702 sendust Inorganic materials 0.000 claims 2
- 238000003756 stirring Methods 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 1
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000002441 X-ray diffraction Methods 0.000 description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000523 sample Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001228 spectrum Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000009616 inductively coupled plasma Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 8
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- GQABSXJCETZGRK-UHFFFAOYSA-N 6-azaniumylhexylazanium;dihydroxide Chemical compound [OH-].[OH-].[NH3+]CCCCCC[NH3+] GQABSXJCETZGRK-UHFFFAOYSA-N 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/50—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the erionite or offretite type, e.g. zeolite T, as exemplified by patent document US2950952
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- B01J35/51—
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- B01J35/615—
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- B01J35/633—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to an ERI type magnesia-silica-alumina molecular sieve, a synthesis method and application thereof. The molecular sieve has the formula of' 1/mMgO.SiO 2 ·1/nAl 2 O 3 "the schematic chemical composition is shown, wherein the silicon-aluminum molar ratio is more than or equal to 10 and less than or equal to 50, and the silicon-magnesium molar ratio is more than or equal to 4 and less than or equal to 50; the ERI type magnesium-silicon-aluminum molecular sieve has an ellipsoidal morphology. The molecular sieve is a pure phase ERI type magnesia-silica-alumina molecular sieve, can be used as an adsorbent or a catalyst for converting organic compounds, and has good performance.
Description
Technical Field
The invention relates to an ERI type magnesia-silica-alumina molecular sieve, a synthesis method and application thereof.
Background
The zeolite has a rich pore system with a certain pore diameter, the pore systems are staggered to form a three-dimensional network structure, and the framework of the zeolite can still exist stably after water or organic matters in the pore systems are removed (US 4439409).The basic framework structure of crystalline microporous zeolite is based on rigid three-dimensional TO 4 (SiO 4 ,AlO 4 Etc.) a unit structure; TO 4 Is to share oxygen atoms in tetrahedral manner, skeleton tetrahedral such as AlO 4 Is balanced by surface cations such as M n+ (e.g. Na + 、K + 、Mg 2+ 、Cu 2+ Etc.) and H + Is maintained in the presence of (a).
Erionite is a natural zeolite with ERI topology structure, the molecular sieve has a three-dimensional communicated 8-membered ring elliptic pore canal structure, and the pore diameter is 0.36 multiplied by 0.51nm. The zeolite and offretite (OFF-type topology) have the same a-axis and b-axis, but have twice as much c-axis as OFF. The ERI type molecular sieve has a unique pore canal structure, and can prepare olefin and CO from methanol 2 The adsorption separation and other applications have excellent performance, so that the adsorption separation and other applications have good commercial value and application prospect, and are attracting a great deal of interest of a plurality of researchers, and molecular sieves including UZM-12, ZSM-34 (intergrowth with OFF), alPO-17, SAPO-17 and SSZ-98 are successfully synthesized at present.
The intergrowth materials of both zeolites are relatively common, patent US 3699139 discloses benzyl trimethylammonium ion as a structure directing agent to synthesize ERI/OFF intergrowth, patent US 4086186 discloses synthesis of ZSM-34 (ERI/OFF intergrowth) with choline, patent CN 101962193a discloses preparation of ZSM-34 molecular sieves with a seed synthesis method.
Patent CN 106241830B discloses that phosphoaluminosapo-17 molecular sieves with ERI configuration are synthesized using cyclohexylamine and the like as structure directing agents, the crystals are hexagonal prism-shaped, and the size is about 1 μm. Tuel et al synthesized AlPO-17 molecular sieves with hexagonal prism-like dimensions of about 100 μm using N, N, N ', N' -tetramethyl-1, 6-hexanediamine as the structure directing agent. Patent CN 106470944B discloses that an SSZ-98 molecular sieve with ERI configuration is synthesized by using N, N' -dimethyl-1, 4-diazabicyclo [2.2.2] octane divalent oxygen ion as a structure directing agent, and crystals are in a rod-like or sheet-like shape, and the size is more than 5 mu m. Patent CN 101072728B discloses a UZM-12 molecular sieve with an ERI configuration of spherical crystals with an average particle size of 15-50 nm. Patent CN 109574034A discloses an ERI type molecular sieve synthesized by an ultrasonic auxiliary method, and the crystal is in a rod shape and has the size of about 500nm.
Disclosure of Invention
The invention aims to provide a novel molecular sieve with an ERI structure and a preparation method thereof.
The first aspect of the present invention provides an ERI-type magnesia-silica-alumina molecular sieve having the formula "1/mMgO.SiO 2 ·1/nAl 2 O 3 "the schematic chemical composition is shown, wherein the silicon-aluminum molar ratio is more than or equal to 10 and less than or equal to 50, and the silicon-magnesium molar ratio is more than or equal to 4 and less than or equal to 50; the ERI type magnesium-silicon-aluminum molecular sieve has an ellipsoidal morphology.
Further, the average length of the ERI type magnesium silicon aluminum molecular sieve crystal is 150-350 nm, and the length-diameter ratio is 1.5-2.5.
Further, the specific surface area of the ERI type magnesia-silica-alumina molecular sieve is 200 to 600 meters 2 Per gram, preferably 250 to 550 meters 2 Per gram, more preferably 300 to 500 meters 2 /g; the micropore volume is 0.04-0.40 cm 3 Per gram, preferably 0.07 to 0.35 cm 3 Per gram, more preferably 0.10 to 0.30 cm 3 /g.
The second aspect of the invention also provides a synthetic method of the ERI type magnesia-silica-alumina molecular sieve, which comprises the steps of uniformly mixing a silicon source, an aluminum source, a magnesium source, an alkali source, a structure directing agent R and water, and carrying out steam water treatment; then heating and crystallizing the mixture to prepare the ERI molecular sieve;
the structure directing agent R is at least one selected from hexamethyldiammonium salt, hexamethyldiammonium hydroxide, pentamethyl ethyl diammonium salt or pentamethyl ethyl diammonium hydroxide.
Further, the structure directing agent R is preferably hexamethyldiammonium hydroxide.
Further, the silicon source (in SiO 2 Calculated as Al), an aluminum source (calculated as Al 2 O 3 Calculated as MgO), a magnesium source (calculated as MgO), an alkali source (calculated as OH - The mol ratio of the structural guiding agent R to the water is 1 (0.05-0.12): 0.02-0.30): 0.10-0.60): 0.05-0.80): 7.5-80, preferably 1 (0.06-0.11): 0.04-0.25): 0.15-0.55): 0.10-0.70): 7.5-60.
Further, the silicon source is at least one selected from silicic acid, silica gel, silica sol, tetraethyl silicate and water glass; the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxide, aluminate, aluminum salt and tetraalkylaluminum; the magnesium source is selected from at least one of magnesium hydroxide, magnesium oxide, aluminate and magnesium salt.
Further, the alkali source is selected from one or more of alkali taking alkali metal as cation.
Further, after the raw material mixture is subjected to a water treatment, a silicon source (SiO 2 Based on the molar ratio of 1 (1-10), preferably 1 (1.5-9), more preferably 1 (2-8) to water.
Further, the method of the distilled water treatment is rotary distilled water or open heated water, and the open heated water treatment condition is that the mixture is heated and stirred at 35-90 ℃, preferably at 40-85 ℃.
Further, the crystallization condition of the mixture is that the mixture is crystallized at 120 to 200 ℃ for 1 to 10 days, preferably at 120 to 180 ℃ for 2 to 9 days, more preferably at 135 to 180 ℃ for 3 to 8 days.
Further, after the crystallization step is completed, the molecular sieve product may be separated from the resulting mixture by any conventionally known separation means. Examples of the separation method include a method of filtering, washing and drying the obtained mixture. Here, the filtering, washing and drying may be performed in any manner conventionally known in the art. As a specific example, as the filtration, for example, the obtained product mixture may be simply suction-filtered. The washing may be performed using deionized water and/or ethanol, for example. The drying temperature is, for example, 40 to 250 ℃, preferably 60 to 150 ℃, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours. The drying may be performed under normal pressure or under reduced pressure.
Further, the molecular sieve prepared according to the foregoing method may be calcined as needed to remove the template agent, moisture which may be present, and the like. The calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature of generally 300 to 800 ℃, preferably 400 to 650 ℃, and a calcination time of generally 1 to 10 hours, preferably 3 to 6 hours. In addition, the calcination is typically performed under an oxygen-containing atmosphere, such as air or an oxygen atmosphere.
In a third aspect the present invention provides a molecular sieve composition comprising an ERI type magnesium silicon aluminium molecular sieve according to any one of the preceding aspects or manufactured according to the manufacturing method of any one of the preceding aspects, and a binder.
In a fourth aspect the present invention provides the use of an ERI-type magnesium alumino-silicate molecular sieve according to any of the preceding aspects, an ERI-type magnesium alumino-silicate molecular sieve composition produced according to the production process according to any of the preceding aspects, as an adsorbent or catalyst for the conversion of organic compounds.
According to the invention, the magnesium-silicon-aluminum molecular sieve has an ERI structure, has regular ellipsoidal morphology and has smaller crystal size.
According to the preparation method provided by the invention, the raw materials are crystallized under the semi-solid state condition, the ERI type molecular sieve with higher purity and uniform particle size is directly synthesized, the actual utilization rate of the reaction kettle is higher (more molecular sieve products are finally obtained in the reaction kettle with unit volume), the cost can be saved, and the advantages are obvious.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the molecular sieve obtained in example 1;
FIG. 3 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 2;
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of the molecular sieve obtained in example 2;
FIG. 5 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 3;
FIG. 6 is an X-ray diffraction pattern (XRD) of the molecular sieve obtained in example 4;
FIG. 7 is a Scanning Electron Microscope (SEM) photograph of the molecular sieve obtained in comparative example 1;
FIG. 8 is a Scanning Electron Microscope (SEM) picture of the molecular sieve obtained in comparative example 3;
FIG. 9 is a Scanning Electron Microscope (SEM) picture of the molecular sieve obtained in comparative example 4;
FIG. 10 is an X-ray diffraction pattern (XRD) of the sample obtained in comparative example 5;
FIG. 11 is an X-ray diffraction pattern (XRD) of the sample obtained in comparative example 6.
Detailed Description
The following detailed description of embodiments of the invention is provided, but it should be noted that the scope of the invention is not limited by these embodiments, but is defined by the claims.
All publications, patent applications, patents, and other references mentioned in this specification are herein incorporated by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art at the time of the application, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present invention, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.
In the context of the present specification, including in the examples and comparative examples below, the micropore volume, specific surface area of the molecular sieve are measured by the nitrogen physical adsorption and desorption method (BET method): the nitrogen physical adsorption and desorption isotherms of the molecular sieve were measured by a physical adsorption instrument (Micromeretic ASAP M2020M physical adsorption instrument), and calculated by BET equation and t-plot equation. The experimental conditions for the MRE type molecular sieve were: the temperature was measured at-169 c and the molecular sieve was vacuum pre-treated for 4 hours at 350 c prior to measurement, while the experimental conditions for the molecular sieve were: the temperature was measured at-169℃and the molecular sieves were heat treated for 6 hours in an air atmosphere at 550℃and then vacuum pre-treated for 4 hours at 350 ℃.
In the context of the present specification, including in the examples and comparative examples below, the molecular sieve X-ray powder diffractometer model Panalytical X PERPRO X-ray powder diffractometer, analysis of the phase of the sample, cuka radiation sourceThe scanning range of 2-50 DEG, the operating voltage is 40KV, the current is 40mA, and the scanning speed is 10 DEG/min.
In the context of the present specification, including in the examples and comparative examples below, the molecular sieves are Scanning Electron Microscopes (SEM) model S-4800 type II field emission scanning electron microscopes. In the context of the present specification, including in the examples and comparative examples below, the method of measuring the crystal length of a molecular sieve is: and (3) observing the molecular sieve under a specific magnification by using an S-4800II type field emission scanning electron microscope, randomly selecting an observation field, and calculating the average value of the sum of the lengths of all crystals in the observation field. This operation was repeated 10 times in total. The diameter of the crystal was calculated by the same method using the average value of the sum of the average values of 10 times as the crystal length.
In the context of this specification, including in the examples and comparative examples below, the inductively coupled plasma atomic emission spectrometer (ICP) model number Varian 725-ES of molecular sieves, the analytical samples were dissolved with hydrofluoric acid to determine the elemental content.
Examples
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Example 1
15.614 g of deionized water, 10.541 g of hexamethyl diammonium hydroxide solution (containing 50 wt.% hexamethyl diammonium) as organic structure directing agent, 13.396 g of silica sol (containing SiO) 2 40 wt%), 3.6431 g of aluminum isopropoxide, 0.520 g of magnesium hydroxide, 0.535 g of sodium hydroxide and 0.751 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours and then is stirred at 80 ℃ in an open way, 17.68 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al 2 O 3 /SiO 2 =0.10
MgO/SiO 2 =0.10
hexamethylenediammonium hydroxide/SiO 2 =0.25
OH - /SiO 2 =0.30
H 2 O/SiO 2 =7
The mixture was placed in a stainless steel reactor and crystallized at 170℃for 7 days. Filtering and washing after crystallization, and drying in a 110 ℃ oven to obtain an XRD spectrum of the molecular sieve, as shown in figure 1, which is a pure phase ERI type magnesia-silica-alumina molecular sieve; the SEM image of the molecular sieve is shown in FIG. 2, the molecular sieve is ellipsoidal, the average length of the crystal is 240nm, and the length-diameter ratio is 2.0.
The specific surface area of the obtained product is 393 meters 2 Per gram, micropore volume 0.16 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =10.2,SiO 2 /MgO=9.7。
Example 2
10.608 g of deionized water, 11.827 g of hexamethyl diammonium hydroxide solution (containing 50 wt.% hexamethyl diammonium) as organic structure directing agent, 12.525 g of silica sol (containing SiO) 2 40 wt%), 3.4062 g of aluminum isopropoxide, 0.365 g of magnesium hydroxide, 0.334 g of sodium hydroxide and 0.936 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours and then is stirred at 60 ℃ in an open way, 12.77 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al 2 O 3 /SiO 2 =0.10
MgO/SiO 2 =0.075
hexamethylenediammonium hydroxide/SiO 2 =0.30
OH - /SiO 2 =0.30
H 2 O/SiO 2 =7.5
The mixture was placed in a stainless steel reactor and crystallized at 180℃for 5 days. Filtering and washing after crystallization, and drying in a 110 ℃ oven to obtain an XRD spectrum of the molecular sieve, as shown in figure 3, which is a pure phase ERI type magnesia-silica-alumina molecular sieve; the SEM image of the molecular sieve is shown in FIG. 4, the molecular sieve is ellipsoidal, the average length of the crystal is 280nm, and the length-diameter ratio is 2.2.
The specific surface area of the obtained product is 391 m 2 Per gram, micropore volume 0.16 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =10.5,SiO 2 /MgO=12.6。
Example 3
7.179 g of deionized water, 12.198 g of hexamethyl diammonium hydroxide solution (containing 50 wt.% hexamethyl diammonium) as organic structure directing agent, 11.072 g of silica sol (containing SiO) 2 40 wt%), 3.0111 g of aluminum isopropoxide, 0.537 g of magnesium hydroxide, 0.590 g of sodium hydroxide and 0.414 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours and then is stirred at 50 ℃ in an open way, 11.29 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al 2 O 3 /SiO 2 =0.10
MgO/SiO 2 =0.125
hexamethylenediammonium hydroxide/SiO 2 =0.35
OH - /SiO 2 =0.30
H 2 O/SiO 2 =6.5
The mixture was placed in a stainless steel reactor and crystallized at 175℃for 6 days. Filtering and washing after crystallization, and drying in a 110 ℃ oven to obtain an XRD spectrum of the molecular sieve, as shown in figure 5, which is a pure phase ERI type magnesia-silica-alumina molecular sieve; SEM image of molecular sieve is similar to that of FIG. 2, molecular sieve is ellipsoidal, average length of crystal is 260nm, and length-diameter ratio is 1.8.
The specific surface area of the obtained product is 385 meters 2 Per gram, micropore volume 0.15 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =10.4,SiO 2 /MgO=8.4。
Example 4
6.342 g deionized water, 9.865 g organic structure directing agent hexamethyl diammonium hydroxide solution (containing 50% by weight of hexamethyl diammonium), 10.446 g silica sol (containing SiO) 2 40 wt%), 2.2728 g of aluminum isopropoxide, 0.406 g of magnesium hydroxide, 0.278 g of sodium hydroxide and 0.390 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours and then is stirred at 50 ℃ in an open way, 10.02 g of water is evaporated, a mixture is prepared, and the final material ratio (molar ratio) is:
Al 2 O 3 /SiO 2 =0.08
MgO/SiO 2 =0.10
hexamethylenediammonium hydroxide/SiO 2 =0.3
OH - /SiO 2 =0.20
H 2 O/SiO 2 =6
The mixture was placed in a stainless steel reactor and crystallized at 165℃for 7 days. Filtering and washing after crystallization, and drying in a 110 ℃ oven to obtain an XRD spectrum of the molecular sieve, as shown in figure 6, which is a pure phase ERI type magnesia-silica-alumina molecular sieve; SEM image of molecular sieve is similar to that of FIG. 2, molecular sieve is ellipsoidal, average length of crystal is 300nm, and length-diameter ratio is 1.9.
The specific surface area of the obtained product is 401 m 2 Per gram, micropore volume 0.17 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =13.2,SiO 2 /MgO=10.4。
Example 5
22.427 g deionized water and 15.962 g organic structureGuide agent hexamethyldiammonium hydroxide solution (containing 50 wt% hexamethyldiammonium hydroxide), 16.903 g silica sol (containing SiO) 2 40 wt%), 2.7581 g of aluminum isopropoxide, 0.328 g of magnesium hydroxide, 0.675 g of sodium hydroxide and 0.947 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours, the raw material liquid is stirred at 85 ℃ in an open way, 29.40 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al 2 O 3 /SiO 2 =0.06
MgO/SiO 2 =0.05
hexamethylenediammonium hydroxide/SiO 2 =0.3
OH - /SiO 2 =0.3
H 2 O/SiO 2 =5.5
The mixture was placed in a stainless steel reactor and crystallized at 160℃for 8 days. Filtering and washing after crystallization, and drying in a baking oven at 110 ℃ to obtain the XRD spectrum of the molecular sieve, which is similar to that of figure 1, and is a pure phase ERI type magnesia-silica-alumina molecular sieve; the SEM of the molecular sieve was similar to that of FIG. 2, the molecular sieve was ellipsoidal, the average length of the crystals was 320nm, and the aspect ratio was 1.8.
The specific surface area of the obtained product is 396 meters 2 Per gram, micropore volume 0.16 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =17.2,SiO 2 /MgO=21.0。
Example 6
8.446 g of deionized water, 10.969 g of an organic structure directing agent hexamethyl diammonium hydroxide solution (containing 50% by weight of hexamethyl diammonium), 11.616 g of silica sol (containing SiO) 2 40 wt%), 1.5796 g of aluminum isopropoxide, 0.902 g of magnesium hydroxide, 0.619 g of sodium hydroxide and 0.868 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours and then is stirred at 75 ℃ in an open way, 13.93 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al 2 O 3 /SiO 2 =0.05
MgO/SiO 2 =0.20
hydrogen oxidationHexamethylenediammonium/SiO 2 =0.30
OH - /SiO 2 =0.40
H 2 O/SiO 2 =5
The mixture was placed in a stainless steel reactor and crystallized at 150 c for 10 days. Filtering and washing after crystallization, and drying in a baking oven at 110 ℃ to obtain the XRD spectrum of the molecular sieve, which is similar to that of figure 1, and is a pure phase ERI type magnesia-silica-alumina molecular sieve; the SEM of the molecular sieve was similar to that of FIG. 2, the molecular sieve was ellipsoidal, the average length of the crystals was 280nm, and the aspect ratio was 2.2.
The specific surface area of the obtained product is 411 m 2 Per gram, micropore volume 0.17 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =20.7,SiO 2 /MgO=5.3。
Example 7
6.329 g of deionized water, 7.262 g of organic structure directing agent hexamethyl diammonium hydroxide solution (containing 50% by weight of hexamethyl diammonium), 9.228 g of silica sol (containing SiO) 2 40 wt%), 1.0039 g of aluminum isopropoxide, 0.538 g of magnesium hydroxide, 0.123 g of sodium hydroxide and 0.517 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours and then is stirred at 50 ℃ in an open way, 9.96 g of water is evaporated, and a mixture is prepared, wherein the final material ratio (molar ratio) is as follows:
Al 2 O 3 /SiO 2 =0.04
MgO/SiO 2 =0.15
hexamethylenediammonium hydroxide/SiO 2 =0.25
OH - /SiO 2 =0.20
H 2 O/SiO 2 =5
The mixture was placed in a stainless steel reactor and crystallized at 170℃for 6 days. Filtering and washing after crystallization, and drying in a baking oven at 110 ℃ to obtain the XRD spectrum of the molecular sieve, which is similar to that of figure 1, and is a pure phase ERI type magnesia-silica-alumina molecular sieve; the SEM of the molecular sieve was similar to that of FIG. 2, the molecular sieve was ellipsoidal, the average length of the crystals was 240nm, and the aspect ratio was 1.7.
The obtained productThe specific surface area of the product is 419 meters 2 Per gram, micropore volume 0.17 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =26.4,SiO 2 /MgO=7.2。
Example 8
11.154 g of deionized water, 18.57 g of a solution of the organic structure directing agent hexamethyl diammonium hydroxide (containing 50% by weight of hexamethyl diammonium), 13.110 g of silica sol (containing SiO) 2 40 wt%), 0.7131 g of aluminum isopropoxide, 0.509 g of magnesium hydroxide, 0.698 g of sodium hydroxide and 0.245 g of potassium hydroxide are mixed uniformly, the raw material liquid is stirred at room temperature for 2 hours and then is stirred at 80 ℃ in an open way, 20.44 g of water is distilled off, a mixture is prepared, and the final material ratio (molar ratio) is:
Al 2 O 3 /SiO 2 =0.02
MgO/SiO 2 =0.10
hexamethylenediammonium hydroxide/SiO 2 =0.45
OH - /SiO 2 =0.25
H 2 O/SiO 2 =5
The mixture was placed in a stainless steel reactor and crystallized at 175℃for 5 days. Filtering and washing after crystallization, and drying in a baking oven at 110 ℃ to obtain the XRD spectrum of the molecular sieve, which is similar to that of figure 1, and is a pure phase ERI type magnesia-silica-alumina molecular sieve; the SEM of the molecular sieve was similar to that of FIG. 2, the molecular sieve was ellipsoidal, the average length of the crystals was 270nm, and the aspect ratio was 2.1.
The specific surface area of the obtained product is 379 m 2 Per gram, micropore volume 0.15 cm 3 /g.
Measurement of SiO of a sample by inductively coupled plasma atomic emission spectrometry (ICP) 2 /Al 2 O 3 =49.2,SiO 2 /MgO=10.5。
Comparative example 1
As in example 1, except that no distilled water treatment step, H 2 O/SiO 2 =18。
The XRD spectrum of the obtained sample is similar to that of figure 1, and is ERI type molecular sieve; the SEM of the molecular sieve is shown in FIG. 7, the molecular sieve has a rod-like morphology, the crystal size is large, and the average length is 5 μm.
Comparative example 2
The same as in example 1, except that no Mg source was added.
The XRD spectrum of the obtained sample is similar to that of figure 1, and is ERI type molecular sieve; the morphology of the molecular sieve is similar to that of comparative example 1, the molecular sieve is in a rod-shaped morphology, the crystal size is large, and the average length is 4 mu m.
Comparative example 3
As in example 3, but without the addition of a source of Mg, baCl was added 2 ,Ba/SiO 2 =0.10。
The XRD spectrum of the obtained sample is similar to that of figure 1, and is ERI type molecular sieve; SEM of the molecular sieve is shown in FIG. 8, the molecular sieve has a rod-like and needle-like morphology, and the average length of the crystals is 2 μm.
Comparative example 4
As in example 5, H was obtained after the steam treatment 2 O/SiO 2 =14。
The XRD spectrum of the obtained sample is similar to that of figure 1, and is ERI type molecular sieve; the SEM of the molecular sieve is shown in FIG. 9, the molecular sieve has a rod-like morphology, and the average length of the crystals is 3 μm.
Comparative example 5
The same procedure as in example 2 was followed except that the organic structure directing agent was N, N, N ', N' -tetramethyl-1, 6-hexanediamine.
The XRD spectrum of the obtained sample is shown in fig. 10, and the sample is not all ERI type molecular sieve (2theta=5.5o is not a characteristic diffraction peak of ERI type molecular sieve).
Comparative example 6
As in example 1, but Al 2 O 3 /SiO 2 =0.01。
The XRD spectrum of the obtained sample is shown in FIG. 11, and the sample does not belong to the ERI type molecular sieve (mainly EUO type structure).
Claims (19)
1. An ERI type magnesia-silica-alumina molecular sieve, which has the formula of' 1/mMgO-SiO 2 ·1/nAl 2 O 3 "the schematic chemical composition is shown, wherein the silicon-aluminum molar ratio is more than or equal to 10 and less than or equal to 50, and the silicon-magnesium molar ratio is more than or equal to 4 and less than or equal to 50;the ERI type magnesium-silicon-aluminum molecular sieve has an ellipsoidal morphology.
2. The ERI type magnesium silicon aluminum molecular sieve according to claim 1, wherein the average length of the ERI type magnesium silicon aluminum molecular sieve crystal is 150-350 nm, and the length-diameter ratio is 1.5-2.5.
3. The ERI type magnesium silicon aluminum molecular sieve according to claim 1, wherein the specific surface area of the molecular sieve is 200-600 meters 2 /g; the micropore volume is 0.04-0.40 cm 3 /g.
4. The ERI type magnesium silicon aluminum molecular sieve according to claim 1, wherein the specific surface area of the molecular sieve is 250-550 meters 2 /g; the micropore volume is 0.07-0.35 cm 3 /g.
5. The ERI type magnesium silicon aluminum molecular sieve according to claim 1, wherein the specific surface area of the molecular sieve is 300-500 m 2 /g; the micropore volume is 0.10-0.30 cm 3 /g.
6. A method for synthesizing an ERI type magnesium-silicon-aluminum molecular sieve according to any one of claims 1 to 5, which is characterized in that a silicon source, an aluminum source, a magnesium source, an alkali source, a structure directing agent R and water are uniformly mixed and distilled; then heating and crystallizing the mixture to prepare the ERI molecular sieve;
the structure directing agent R is at least one selected from hexamethyldiammonium salt, hexamethyldiammonium hydroxide, pentamethyl ethyl diammonium salt or pentamethyl ethyl diammonium hydroxide;
the silicon source is SiO 2 For counting, aluminum source is Al 2 O 3 Calculated by MgO as magnesium source and OH as alkali source - The mol ratio of the structural guiding agent R to water is 1 (0.05-0.12): (0.02-0.30): (0.10-0.60): (0.05-0.80): (7.5-80);
after the raw material mixture is subjected to water steaming treatment, the silicon source is prepared from SiO during crystallization 2 For measuring and waterThe molar ratio is 1 (1-10).
7. The method of synthesis according to claim 6, wherein the silicon source is in the form of SiO 2 For counting, aluminum source is Al 2 O 3 Calculated by MgO as magnesium source and OH as alkali source - The molar ratio of the structural guiding agent R to water is 1 (0.06-0.11): (0.04-0.25): (0.15-0.55): (0.10-0.70): (7.5-60).
8. The method according to claim 6, wherein the silicon source is at least one selected from the group consisting of silicic acid, silica gel, silica sol, tetraethyl silicate, and water glass; the aluminum source is selected from at least one of aluminum hydroxide, aluminum oxide, aluminate, aluminum salt and tetraalkylaluminum; the magnesium source is selected from at least one of magnesium hydroxide, magnesium oxide and magnesium salt.
9. The method according to claim 6, wherein the alkali source is one or more selected from alkali metal cations.
10. The method according to claim 6, wherein the structure directing agent R is hexamethyl diammonium hydroxide.
11. The synthesis method according to claim 6, wherein the silicon source is SiO during crystallization after the raw material mixture is subjected to water distillation 2 The molar ratio of the water to the water is 1 (1.5-9).
12. The synthesis method according to claim 6, wherein: after the raw material mixture is subjected to water steaming treatment, the silicon source is prepared from SiO during crystallization 2 The molar ratio of the water to the water is 1 (2-8).
13. The synthesis method according to claim 6, wherein the method of steaming water treatment is spin steaming water or open heating water removal, and the open heating treatment condition is heating and stirring at 35-90 ℃.
14. The synthesis method according to claim 6, wherein the method of steaming water treatment is spin steaming water or open heating water removal, and the open heating treatment condition is heating and stirring at 40-85 ℃.
15. The method of synthesis according to claim 6, wherein the crystallization conditions of the reaction mixture include: crystallizing at 120-200 ℃ for 1-10 days.
16. The method of synthesis according to claim 6, wherein the crystallization conditions of the reaction mixture include: crystallizing at 120-180 ℃ for 2-9 days.
17. The method of synthesis according to claim 6, wherein the crystallization conditions of the reaction mixture include: crystallizing at 135-180 ℃ for 3-8 days.
18. An ERI-type sendust molecular sieve composition comprising an ERI-type sendust molecular sieve according to any one of claims 1-5 or an ERI molecular sieve synthesized according to the synthesis method of claims 6-17, and a binder.
19. Use of an ERI type magnesium silicon aluminum molecular sieve according to any one of claims 1 to 5, a silicon aluminum molecular sieve synthesized according to the synthesis method of any one of claims 6 to 17, or a molecular sieve composition according to claim 18 as an adsorbent or a catalyst for conversion of organic compounds.
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