CN115231583A - ERI framework single crystal molecular sieve and preparation method and application thereof - Google Patents
ERI framework single crystal molecular sieve and preparation method and application thereof Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 112
- 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 112
- 239000013078 crystal Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 7
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical group CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000009466 transformation Effects 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 46
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 37
- 238000002425 crystallisation Methods 0.000 claims description 31
- 230000008025 crystallization Effects 0.000 claims description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003463 adsorbent Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910002796 Si–Al Inorganic materials 0.000 claims 1
- 239000002149 hierarchical pore Substances 0.000 abstract description 22
- 239000011148 porous material Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 16
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 16
- 229910052753 mercury Inorganic materials 0.000 description 16
- -1 aluminum ions Chemical class 0.000 description 14
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 description 13
- 238000010791 quenching Methods 0.000 description 11
- 230000000171 quenching effect Effects 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910017119 AlPO Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- XDIAMRVROCPPBK-UHFFFAOYSA-N 2,2-dimethylpropan-1-amine Chemical compound CC(C)(C)CN XDIAMRVROCPPBK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- TYJQMJYIXSXHBO-UHFFFAOYSA-N 1-azabicyclo[2.2.2]octane Chemical compound C1CC2CCN1CC2.C1CC2CCN1CC2 TYJQMJYIXSXHBO-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000215777 Plumeria rubra Species 0.000 description 1
- 235000013087 Plumeria rubra Nutrition 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052677 heulandite Inorganic materials 0.000 description 1
- 238000001198 high resolution scanning electron microscopy Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
- C01B37/08—Silicoaluminophosphates [SAPO compounds], e.g. CoSAPO
-
- 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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/17—Pore diameter distribution
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Abstract
The invention relates to an ERI framework single crystal molecular sieve and a preparation method and application thereof. The ERI framework single crystal molecular sieve is in a hexagonal prism shape in the shape of an integral single crystal; macropores exist in the single crystal morphology, and the diameter of the macropores is 100nm-300nm. The invention is prepared by taking an AFI structure molecular sieve as a precursor and carrying out crystal transformation in the presence of a template agent R, wherein R is N, N, N ', N' -tetramethyl hexanediamine. The invention prepares the hierarchical pore and ERI framework single crystal molecular sieve. The preparation process is simple, the step of preparing the hierarchical holes by conventional post-treatment is omitted, the cost of energy, manpower, time and the like is saved, and the method has good industrial application value.
Description
Technical Field
The invention relates to an ERI framework single crystal molecular sieve and a preparation method and application thereof, in particular to an ERI framework single crystal molecular sieve with hierarchical pores and a preparation method and application thereof.
Background
In 1954, the united states of america combined carbide company developed artificially synthesized zeolite molecular sieves for the first time, and since then, the synthesis and application of various zeolite molecular sieves were rapidly developed. Wilson S.T. and Flarigen E.M. of the company were successful in 1982 in developing a completely new family of molecular sieves- -aluminum phosphate AlPO 4 N (n is a number), which is an important milestone in the development history of molecular sieves, breaking the conventional concept that zeolite molecular sieves consist of silicon-oxygen tetrahedra and aluminum-oxygen tetrahedra, which are well known in the past. AlPO resulting from the combination of trivalent aluminum ions and trivalent phosphate 4 Molecular sieves are electrically neutral, have very weak surface acidity, and do not have ion exchange properties, and thus lack the so-called "active sites" required for catalytic reactions. In 1984, lok et al introduced tetravalent Si into AlPO 4 In the molecular sieve framework, a series of silicoaluminophosphate molecular Sieves (SAPO) with certain acidity are synthesized. SAPO-17 is a heulandite structure molecular sieve, a small pore molecular sieve belonging to the ERI structure type (Acta crystallogr, C42,283-286 (1986)). The structure has three-dimensional eight-membered ring channels, the effective aperture is about 0.36 multiplied by 0.51nm, and the structure can be used for preparing high CO 2 Membrane separation material (Journal of Membrane Science 520 (2016) 507-514) with separation performance for separating CO from natural gas and flue gas 2 A gas. In addition, the catalyst has small pore channels, high specific surface area and moderate Bronsted acid center, so the catalyst has good catalytic effect in MTO reaction, can obtain low-carbon olefin with high yield and has higher ethylene/propylene ratio (Natural Gas Conversion II 1994 Elsevier Science B.V.393-398), and has important significance for synthesis of ERI framework in view of the aboveThe significance of (1).
In addition, because the pore size of the microporous molecular sieve is relatively small, mass transfer and heat transfer of a reaction system are often limited when the microporous molecular sieve is used as a catalyst, so that the activity and the service life of the catalyst are influenced, the defect can be further overcome by reducing the crystal size and modulating the crystal pore structure, and great interest of researchers is aroused by synthesizing nano small crystal grains, nano flaky crystal grains and the like. Generally, a material having a pore size ranging from 2nm or less is called a micro pore (micropore), a material having a pore size ranging from 2 to 50nm is called a meso pore (mesopore), a material having a pore size greater than 50nm is called a macro pore, and a material having two or three pore sizes and communicating with each other is called a hierarchical pore material. The hierarchical pore molecular sieve (catalyst) combines the microporous property of the molecular sieve (catalyst) and the mesopore and/or macropore system, so that guest molecules in the reaction system can be promoted to be more easily close to an active center and be more easily transferred and diffused, the reaction activity, the service life, the selectivity and the like of the catalyst are greatly improved, the utilization efficiency of the catalyst is improved, the energy consumption is reduced, raw materials are saved, the cost is saved and the like (DOI: 10.1021/acs. Chemrev. 0c00016), and therefore, the synthesis of the hierarchical pore SAPO-17 molecular sieve has extremely important practical significance.
In the embodiment 25 of the US patent 4440871, quinuclidine (quinuclidine) is used as a template agent, and the sol ratio is 0.6SiO 2 :1.3Al 2 O 3 :1P 2 O 5 :60H 2 And O, obtaining SAPO-17 containing a small amount of impurities (with XRD diffraction peaks at 2 theta =7.75, 13.4, 15.55, 20.6, 40.0, 40.3 and 52.3, and unknown impurity peaks) in 338 hours at 200 ℃. In example 26, cyclohexylamine was used as a template, aluminum isopropoxide and phosphoric acid were used as an aluminum source and a phosphorus source, and silica sol was used as a silicon source, and the sol ratio was 1.0cha 2 :Al 2 O 3 :P 2 O 5 :50H 2 And O, crystallizing at 200 ℃ for 50 hours to obtain SAPO-17 containing a small amount of impurities.
JOSEPH J. (Acta Crystal., 1986. C42, 283-286) piperidine (piperidine) was added to an aluminum phosphate sol as a template for AlPO-17 synthesis and crystallized at 200 ℃ for one week to give AlPO-17 in the form of hexagonal prism (0.018X 0.16 mm), butContaining small amount of analcime and AlPO 4 -15。
U.S. Pat. No. 4,477,8780 (1988) uses N, N, N, N ', N ', N ' -hexamethyl hexamethylene diammonium hydroxide as template agent, and the pure SAPO-17 is prepared by crystallization at 180 ℃ for 4 days. Qiming Gao et al (j. Chem. Soc., chem. Commu., 1994, 1465-1466) 1.0a1 in a non-aqueous system using methylamine as a template and aluminum isopropoxide and phosphoric acid as sources of aluminum and phosphorus 2 O 3 :1.8P 2 O 3 :13.4MeNH 2 13.4MeOH, 88.0 ethylenglycol, 180 ℃ for 5 days, and AlPO-17 was successfully synthesized. Qingling Liu et Al (Chem Sus Chem 2011,4, 91-97) use neopentyl amine as template agent, aluminium isopropoxide and phosphoric acid as aluminium source and phosphorus source, and the sol proportion is Al 2 O 3 :P 2 O 5 :neopentylamine:H 2 O =1 2 AlPO-17 of (1).
Korea Shuyun et al (advanced chemical science, 8.1988, volume 9, 838-840) uses cyclohexylamine as template agent, aluminium hydroxide and aluminium isopropoxide as aluminium source, ethyl orthosilicate, white carbon black and silica sol as silicon source to conduct crystallization research, and preferably uses aluminium hydroxide and white carbon black as aluminium source and silicon source at given temperature (150 ℃ -200 ℃), so that SAPO-17 hexagonal prism-shaped crystals with the length of about 62 μm can be prepared. Plumeria rubra, etc. (a novel chemical material, 4 months 2015, 4 th period 43, 166-168.), 0.11 percent of sol by using cyclohexylamine as a template agent, silica sol as a silicon source and aluminum isopropoxide as an aluminum Source (SiO) 2 ):1(Al 2 O 3 ):1(P 2 O 5 ):1(CHA):50(H 2 O) and crystallizing for 4 days at 200 ℃ to synthesize SAPO-17 without crystal impurities. Xujun (Tianjin chemical industry, 2016 (5 months) and 30 (3 rd) th period, 17-19) and the like, takes pseudo-boehmite as an aluminum source, phosphoric acid as a phosphorus source, silica sol as a silicon source, cyclohexylamine as a template agent and hydrofluoric acid as a fluorine source, and the mixture ratio of the raw materials is 1Al 2 O 3 :1P 2 O 5 :0.3SiO 2 :1CHA:1HF:40H 2 And O, crystallizing at 200 ℃ for 72 hours to synthesize the pure SAPO-17 molecular sieve. Xiaona Liu et al (Chinese Journal of Catalysis 41 (2020), 1715-1722) use cyclohexylamine as a template and zeolite molecular sieve (providing silicon) is addedSource) synthesis of SAPO-17.
Adding appropriate amount of KCl after HF addition in modern chemical engineering, 1Al under optimized experimental conditions, queen-culture et Al (5 months in 2018, vol. 38, no. 5, 159-163) 2 O 3 :1P 2 O 5 :0.1SiO 2 :1.1CHA:50H 2 O: 0.9HF.
Chinese patent CN106241830A (2014) discloses that a nanometer T-type molecular sieve with the same framework structure as that of SAPO-17 is used as a crystalline silicon source for synthesizing the SAPO-17 molecular sieve, so as to synthesize submicron SAPO-17 molecular sieve crystals with high crystallinity.
From the above disclosure, it can be seen that the following problems exist in the synthesis of SAPO-17:
1. the method is easy to accompany with impure phase, and pure ERI framework molecular sieve crystal is not easy to obtain;
2. the ratio of silicon to aluminum is low, and can not break through 0.1, namely SiO is more than or equal to 0 2 /Al 2 O 3 ≤0.1；
3. The obtained crystal particles are relatively large, and the size uniformity is not easy to control;
4. in order to obtain the hierarchical porous material, post-treatment with acid, alkali and the like is generally required.
In order to adapt to the industrial application of SAPO-17 or AlPO-17, the synthesis of ERI framework molecular sieves with pure phases, hierarchical pores and adjustable silicon content in a larger content range becomes an important problem to be solved urgently in the prior art.
Disclosure of Invention
In view of the shortcomings of the prior art, the first object of the present invention is to provide a hierarchical porous ERI framework single crystal molecular sieve; the second purpose of the invention is to provide a preparation method of the hierarchical pore ERI framework single crystal molecular sieve. The third purpose of the invention is to provide an application of the hierarchical pore ERI framework single crystal molecular sieve.
The inventor of the invention finds that when the AFI structure molecular sieve is used as a precursor and N, N, N ', N' -hexamethylene diamine is used as a template for crystal transformation, the single crystal molecular sieve with hierarchical pores and an ERI structure can be rapidly prepared, so that the problems in the aspects mentioned above are solved at one time.
The first aspect of the invention provides an ERI framework single crystal molecular sieve, wherein the molecular sieve is in a hexagonal prism shape in the overall single crystal appearance; macropores exist in the single crystal morphology, and the diameter of the macropores is 100nm-300nm.
Further, the BET area of the ERI framework single crystal molecular sieve is 410-490cm 2 G, preferably from 410 to 460cm 2 /g。
Further, the hexagonal prism-like morphology has a diameter of 0.8-1.5 μm, preferably 1.1-1.5 μm, and a length of 3-7 μm.
The ERI framework single crystal molecular sieve silicon-aluminum substance weight ratio is as follows: siO is not less than 0 2 /Al 2 O 3 0.2 or less, preferably 0 or less SiO 2 /Al 2 O 3 0.18 or less, more preferably 0.02 or less SiO 2 /Al 2 O 3 ≤0.1。
The macropores in the molecular sieve and the inherent pore channels of the molecular sieve jointly form a hierarchical pore structure.
The invention provides a preparation method of the ERI framework single crystal molecular sieve, which comprises the step of taking the molecular sieve with the AFI structure as a precursor, and carrying out crystal transformation in the presence of a template agent R to prepare the ERI framework single crystal molecular sieve, wherein the R is N, N, N ', N' -tetramethyl hexanediamine.
Further, the preparation method of the ERI framework single crystal molecular sieve comprises the following steps:
1) Fully mixing a template agent R with water to obtain a mixed solution I;
2) Adding an AFI structure molecular sieve into the mixed solution I under stirring to obtain a mixed solution II;
optionally adding ERI seed crystals and/or optionally adding phosphoric acid and/or hydrofluoric acid solution as an additive in the step 1) or the step 2); wherein the mass ratio of each substance in the mixed solution II is as follows:
5AFI:(2.1-4.3)R:(0-0.1)ERI:(0-0.5)H 3 PO 4 :(0-0.1)HF:(15-30)H 2 O；
3) Crystallizing the mixed liquid II obtained in the step 2) to obtain the ERI framework single crystal molecular sieve.
Furthermore, the added amount of the ERI seed crystals is preferably 5AFI (0.03-0.1) ERI. The ERI seed crystal is a molecular sieve or a T-type molecular sieve with an ERI structure, and preferably SAPO-17.
Further, the AFI structural molecular sieve is selected from SAPO-5 and/or AlPO-5 molecular sieves. The amount of AFI is calculated as either aluminum phosphate or silicoaluminophosphate.
Further, the quantity ratio of the silicon-aluminum substance of the AFI structure molecular sieve is up to 0.2, namely SiO is more than or equal to 0 2 /Al 2 O 3 ≤0.2。
Further, after the AFI structure molecular sieve is added in the step 2), the mixture is preferably stirred for 2-4 h at room temperature.
Further, the conditions of the crystallization treatment are as follows: the crystallization temperature range: 190-210 ℃, preferably 195 ℃ -205 ℃, crystallization time: 1h to 60h, preferably 2 to 48h. The crystallization is carried out in a crystallization kettle with a polytetrafluoroethylene lining, and a dynamic crystallization mode is preferably adopted.
Further, it is preferable to carry out drying and baking processes after crystallization, which are conventionally performed. The drying conditions are as follows: the temperature is 50-120 ℃, preferably 80-100 ℃, and the drying time is 10-30h, preferably 12-24h; the roasting condition is that the roasting temperature is 450-650 ℃, preferably 500-600 ℃, and the roasting time is 3-10 hours, preferably 4-6 hours.
In a third aspect, the invention provides an application of the ERI framework single crystal molecular sieve as an adsorbent or a catalyst component.
The invention uses the molecular sieve with AFI framework structure as a precursor and uses NNN 'N' -tetramethyl hexanediamine as a template agent, better solves the defects of the prior art and prepares the ERI framework single crystal molecular sieve with hierarchical pores. The ERI framework single crystal molecular sieve has the advantages of simple preparation process, readily available raw materials and good repeatability, and can be used as an adsorbent or a catalyst component in actual industrial production, such as carbon dioxide adsorption separation, MTO and other reactions. The technical means of the invention can solve the problem that the prior synthesis is easy to accompany heterogeneous phase and silicon-aluminum (SiO) at one time 2 /Al 2 O 3 ) The problems that the high-silicon-aluminum ratio molecular sieve cannot be obtained in a narrow proportion range, a multilevel hole can be obtained only through post-treatment and the like are solved, and raw materials are savedThe cost such as energy saving, time saving and the like, and has good industrial application prospect.
Drawings
FIG. 1: XRD pattern of precursor SAPO-5 with charge ratio of 0.06;
FIG. 2 is a schematic diagram: SEM picture of precursor SAPO-5 with feed ratio of 0.06;
FIG. 3: XRD pattern of seed crystal SAPO-17;
FIG. 4 is a schematic view of: SEM image of seed crystal SAPO-17;
FIG. 5 is a schematic view of: XRD pattern of the prepared molecular sieve of example 1;
FIG. 6: SEM image of the molecular sieve prepared in example 1;
FIG. 7 is a schematic view of: example 1N of the prepared molecular sieves 2 Isothermal adsorption drawing;
FIG. 8: mercury intrusion data plot for molecular sieve prepared in example 1;
FIG. 9: macropore size distribution profile for the molecular sieve prepared in example 1;
FIG. 10: XRD pattern of the prepared molecular sieve of example 4;
FIG. 11: SEM image of the molecular sieve prepared in example 4;
FIG. 12: XRD pattern of the prepared molecular sieve of example 7;
FIG. 13 is a schematic view of: SEM image of the molecular sieve prepared in example 7;
FIG. 14: XRD pattern of the molecular sieve prepared in comparative example 1;
FIG. 15: SEM image of the molecular sieve prepared in comparative example 1.
Detailed Description
The invention will be further illustrated and described with reference to specific examples, but it should be understood that the scope of the invention is not limited to the specific examples. The test equipment and conditions used for the various properties in the examples are as follows:
XRD: the phase of the sample was analyzed using an X-ray powder diffractometer model PANalytical X' Pert PRO, parnaciaceae, netherlands, (light pipe: target-transferring Cu target,
voltage and current: 40kv × 40ma), 2 θ scan range: 2-50 degree, scanning speedDegree of 7 DEG/min -1 。
SEM the crystal morphology was analyzed by high resolution scanning electron microscopy using Hitachi S-4800, FEI, japan. Magnification factor: 40-1000000 x, and the accelerating voltage is 3.0KV.
ICP-AES analysis of the elemental ratio of a sample was carried out by using an inductively coupled plasma emission spectrometer of the Varian analytical 725-ES model, varian Analytica, varian.
N 2 Adsorption-desorption: the N of the samples was determined at 77K using a full-automatic specific surface and porosity analyzer model ASAP2020M TriStar 3000 from Mac instruments USA 2 Adsorption-desorption isotherms, measurable pore size range:
specific surface area: not less than 0.01m 2 /g(N 2 Adsorption), surface area: not less than 0.0001m 2 (ii)/g (Kr adsorption). And (4) calculating the pore volume and the specific surface area of the micropore by adopting a t-plot method.
And (3) macroporous analysis: a mercury intrusion type pore size analyzer Pascal 140/240 (Thermo Electron) is adopted; the technical indexes are as follows: pore size of Pascal140 low-pressure mercury intrusion instrument: pressure range of 116 to 3.8 μm: 0.1-400 KPa. Pore size of Pascal 240 high-pressure mercury porosimeter: maximum pressure of 15-0.0074 μm: 200MPa.
Preparation of a precursor AFI:
the silicon-aluminum charge ratio is 0.1 (SiO) 2 /Al 2 O 3 The mol ratio is 0.1), and the specific preparation process of the SAPO-5 comprises the following steps: 188g of water is weighed, 30.2g of pseudo-boehmite is added under the stirring, 46.12g of phosphoric acid is then added, water bath at 70 ℃ is added, the stirring is carried out for 2h, 3.25g of Ludox-40 percent is added under the stirring, 24.28g of triethylamine is added after the uniform stirring, the stirring is continued for 2h, and then the mixture is transferred to a crystallization kettle and crystallized for 30h at 200 ℃. Taking out, quenching, centrifuging, washing (repeating for 2-3 times), and oven drying. Under the condition that the content of silicon is only changed under other conditions, the SAPO-5 molecular sieve with the silicon-aluminum ratio of 0-0.2 can be prepared, and dried at 80 ℃ for later use. FIG. 1 shows the charge ratio (SiO) 2 /Al 2 O 3 Mole ratio) of 0.06 of the precursor SAPO-5; FIG. 2 shows the charge ratio (SiO) 2 /Al 2 O 3 In a molar ratio) ofSEM image of 0.06 precursor SAPO-5.
Preparation of SAPO-17 seed crystal:
30g of water is weighed, 11.53g of phosphoric acid is added, 7.2g of pseudo-boehmite is added after uniform stirring, a mixture of 0.4g of Ludox-40% and 10g of water is added after sufficient stirring, then 5g of cyclohexylamine and a mixture of 2.5g of triethylamine and 20g of water are added, and stirring is carried out for a certain time. Then placing the mixture into a rotary oven at 210 ℃ for crystallization for 20 hours. Taking out, centrifugally separating, washing, drying and roasting at 550 ℃ for 6 hours for later use. FIG. 3 gives the XRD pattern of the seed SAPO-17; figure 4 gives an SEM picture of seed SAPO-17.
For convenience of description, the templating agents described in the examples below are all N, N, N ', N' -tetramethylhexamethylenediamine.
[ example 1 ]
Weighing 25g of water, adding 4.3g of template agent, fully dissolving, and adding 5g of silicon-aluminum feed ratio (SiO) 2 /Al 2 O 3 Mole ratio) of 0.03, fully mixing the unbaked SAPO-5 molecular sieve precursors, and stirring for 3 hours at room temperature; adding 0.25g of 40 percent HF solution under stirring, uniformly stirring, transferring the mixture to a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 45 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.02,bet area: 457cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
FIG. 5 shows an XRD pattern of the molecular sieve prepared in this example; FIG. 6 shows an SEM image of the molecular sieve; FIG. 7 shows the N of the molecular sieve 2 Isothermal adsorption of the figure; FIG. 8 is a graph of mercury intrusion data for the molecular sieve; it can be seen from fig. 8 that macropores are present in the molecular sieve. The macroporous pore size distribution of the molecular sieve is given in fig. 9.
[ example 2 ]
Weighing 25g of water, adding 4.3g of template agent, fully dissolving, and adding 5g of silicon-aluminum material with a feed ratio (SiO) 2 /Al 2 O 3 Mole ratio) of 0.03 and 0.05g of raw powder of SAPO-5 molecular sieve and stirring at room temperature for 3h. Adding 0.25g of 40 percent HF solution into the mixed solution under stirring, uniformly stirring, transferring the mixed solution into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at the temperature of 200 ℃, crystallizing for 42 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.06,bet area: 440cm 2 (iv) g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 3 ]
Weighing 25g of water, adding 4.3g of template agent and 0.03g of SAPO-17 raw powder, fully mixing, and adding 5g of silicon-aluminum material with a feed ratio (SiO) 2 /Al 2 O 3 Mole ratio) of 0.1, stirring at room temperature for 3h; adding 0.25g of 40 percent HF solution under stirring, uniformly stirring, transferring the mixture to a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at the temperature of 200 ℃, crystallizing for 36 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.09,bet area: 449cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 4 ] A method for producing a polycarbonate
Weighing 25g of water, adding 4.3g of template agent and 0.05g of SAPO-17 roasted raw powder, fully mixing, and adding 5g of silicon-aluminum batch ratio (SiO) 2 /Al 2 O 3 Mole ratio) of 0.2, stirring at room temperature for 3h, adding 0.25g and 40% HF solution under stirring, transferring to a crystallization kettle with a polytetrafluoroethylene lining after uniformly stirring, placing in a rotary oven at 200 ℃ for crystallization for 40h, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.17,bet area: 456cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 5 ]
Weighing 25g of water, adding 0.5g of phosphoric acid, 4.3g of template agent and 0.1g of AlPO-17 roasting raw powder, fully mixing, adding 5g of non-roasted AlPO-5 molecular sieve precursor, stirring at room temperature for 3 hours, adding 0.1g of 40% HF solution under stirring, and uniformly stirring to obtain a mixed solution III; and then transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at 200 ℃, crystallizing for 40 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0,bet area: 415cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 6 ]
Weighing 15g of water, adding 4.3g of template agent and 5g of silicon-aluminum feed ratio (SiO) 2 /Al 2 O 3 Mole ratio) of 0.06, adding 0.05g of SAPO-17 raw powder after fully mixing, and stirring for 5h at room temperature; adding 0.25g of HF solution under stirring, uniformly stirring, transferring to a crystallization kettle with a polytetrafluoroethylene lining, putting into a rotary oven at 200 ℃, crystallizing for 12 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.056,bet area: 435cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 7 ] A method for producing a polycarbonate
Weighing 15g of water, 4.3g of template agent and 0.05g of SAPO-17 raw powder, uniformly stirring, and adding 5g of silicon-aluminum with a feed ratio (SiO) 2 /Al 2 O 3 Molar ratio) of 0.06, stirring at room temperature for 3h, transferring to a crystallization kettle with a polytetrafluoroethylene lining, placing into a rotary oven at 210 ℃, crystallizing at the temperature for 12h, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.057,bet area: 425cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shapedThe diameter is about 1.1-1.5 μm and the length is 3-7 μm.
[ example 8 ]
Weighing 20g of water, adding 0.5g of phosphoric acid and 5g of unfired SAPO-5 molecular sieve precursor with the silicon-aluminum batch ratio of 0.06, fully mixing, adding 4.3g of template agent, and stirring at room temperature for 3 hours; adding 0.25g of HF solution under stirring, uniformly stirring, transferring to a crystallization kettle with a polytetrafluoroethylene lining, putting into a rotary oven at 210 ℃, crystallizing for 2 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.058,bet area: 430cm 2 (iv) g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 9 ]
20g of water are weighed in, 0.5g of phosphoric acid and 5g of silicon-aluminium batch ratio (SiO) are added 2 /Al 2 O 3 Molar ratio) of 0.06, adding 4.3g of template agent after fully mixing, and stirring for 3h at room temperature; adding 0.25g of HF solution under stirring, uniformly stirring, transferring to a crystallization kettle with a polytetrafluoroethylene lining, putting into a rotary oven at 190 ℃, crystallizing for 48 hours at the temperature, taking out, rapidly cooling, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.054,bet area: 442cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 10 ]
Weighing 15g of water, adding 2.2g of template agent, stirring uniformly, and adding 5g of silicon-aluminum feed ratio (SiO) 2 /Al 2 O 3 Molar ratio) of 0.06, adding 0.05g of SAPO-17 roasted raw powder after fully mixing, and stirring for 3h at room temperature; adding 0.25g of HF solution under stirring, uniformly stirring, transferring to a crystallization kettle with a polytetrafluoroethylene lining, putting into a rotary oven at 200 ℃, crystallizing for 36 hours at the temperature, taking out, rapidly cooling, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.028, bet area: 433cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
[ example 11 ]
Weighing 15g of water, adding 0.2g of phosphoric acid and 5g of silicon-aluminum according to the feeding ratio (SiO) 2 /Al 2 O 3 The mol ratio) of 0.06, roasting the SAPO-5 molecular sieve precursor for 4h at 550 ℃, fully mixing, adding 4.3g of template agent, and stirring for 3h at room temperature; adding 0.25g of HF solution under stirring, uniformly stirring, transferring to a crystallization kettle with a polytetrafluoroethylene lining, putting into a rotary oven at 200 ℃, crystallizing for 36 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the hierarchical pore and ERI framework single crystal molecular sieve. SiO 2 2 /Al 2 O 3 =0.059,bet area: 448cm 2 (ii)/g; mercury intrusion macropore distribution: 100nm-300nm. The single crystal is hexagonal prism-shaped, and has a diameter of about 1.1-1.5 μm and a length of 3-7 μm.
Comparative example 1
25g of water and 5g of silicon-aluminum are weighed and added, and the feed ratio of silicon to aluminum (SiO) is increased 2 /Al 2 O 3 Mole ratio) of 0.03, and fully mixing to obtain a mixed solution I; then adding 2.5g of cyclohexylamine into the mixed solution I, and stirring for 4 hours at room temperature to obtain mixed solution II; adding 0.25g of HF solution into the mixed solution II under stirring, and uniformly stirring to obtain a mixed solution III; and then transferring the mixed solution III into a crystallization kettle with a polytetrafluoroethylene lining, putting the crystallization kettle into a rotary oven at the temperature of 200 ℃, crystallizing for 24 hours at the temperature, taking out, quenching, centrifuging, washing and drying to obtain the molecular sieve which mainly comprises SAPO-17 and has a diffraction peak at a low angle, wherein the shape of the obtained SAPO-17 is not porous.
Claims (12)
1. The ERI framework single crystal molecular sieve is characterized in that the molecular sieve is in a hexagonal prism shape in the overall single crystal appearance; macropores exist in the single crystal morphology, and the diameter of the macropores is 100nm-300nm.
2. The ERI framework single crystal molecular sieve of claim 1, whereinThe BET area of the ERI framework single crystal molecular sieve is 410-490cm 2 G, preferably from 410 to 460cm 2 /g。
3. The ERI framework single crystal molecular sieve according to claim 1, characterized in that the hexagonal prism-like morphology is 0.8-1.5 μ ι η in diameter, preferably 1.1-1.5 μ ι η, and 3-7 μ ι η in length.
4. The ERI framework single crystal molecular sieve of claim 1, wherein the ERI framework single crystal molecular sieve has a silicon-aluminum species mass ratio of: siO is not less than 0 2 /Al 2 O 3 0.2 or less, preferably 0 or less SiO 2 /Al 2 O 3 0.18 or less, more preferably 0.02 or less of SiO 2 /Al 2 O 3 ≤0.1。
5. The preparation method of the ERI framework single crystal molecular sieve of any one of claims 1 to 4, characterized in that the ERI framework single crystal molecular sieve is prepared by taking the molecular sieve with AFI structure as a precursor and carrying out crystal transformation in the presence of a template agent R, wherein R is N, N, N ', N' -tetramethyl hexanediamine.
6. The preparation method of claim 5, wherein the preparation method of the ERI framework single crystal molecular sieve comprises the following steps:
1) Fully mixing the template agent R with water to obtain a mixed solution I;
2) Adding an AFI structure molecular sieve into the mixed solution I under stirring to obtain a mixed solution II;
optionally adding ERI seed crystals and/or optionally adding phosphoric acid and/or hydrofluoric acid solution as an additive in the step 1) or the step 2); wherein the mass ratio of each substance in the mixed solution II is as follows:
5AFI:(2.1-4.3)R:(0-0.1)ERI:(0-0.5)H 3 PO 4 :(0-0.1)HF:(15-30)H 2 O；
3) Crystallizing the mixed liquid II obtained in the step 2) to obtain the ERI framework single crystal molecular sieve.
7. The method according to claim 6, wherein the ERI seed is added in an amount of 5AFI (0.03-0.1) ERI.
8. The preparation method according to claim 6 or 7, characterized in that the ERI seeds are molecular sieves with ERI structure or T-type molecular sieves, preferably SAPO-17.
9. The preparation process according to claim 5 or 6, characterized in that the AFI structured molecular sieve is selected from SAPO-5 and/or AlPO-5 molecular sieves.
10. The preparation method according to claim 5 or 6, wherein the AFI structured molecular sieve Si-Al material is present in an amount ratio of 0 ≤ SiO 2 /Al 2 O 3 ≤0.2。
11. The method according to claim 6, wherein the crystallization treatment is performed under the following conditions: crystallization temperature range: 190-210 ℃, preferably 195 ℃ -205 ℃; crystallization time: 1h to 60h, preferably 2 to 48h.
12. Use of the ERI framework single crystal molecular sieve of any one of claims 1 to 4 or the ERI framework single crystal molecular sieve prepared by the method of any one of claims 5 to 11 as an adsorbent or catalyst component.
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