CN107848823A - 硅铝酸盐lev骨架类型沸石的合成 - Google Patents
硅铝酸盐lev骨架类型沸石的合成 Download PDFInfo
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- CN107848823A CN107848823A CN201680041793.9A CN201680041793A CN107848823A CN 107848823 A CN107848823 A CN 107848823A CN 201680041793 A CN201680041793 A CN 201680041793A CN 107848823 A CN107848823 A CN 107848823A
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- 239000010457 zeolite Substances 0.000 title claims abstract description 71
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 44
- 230000015572 biosynthetic process Effects 0.000 title claims description 17
- 238000003786 synthesis reaction Methods 0.000 title claims description 17
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims description 6
- 150000001768 cations Chemical class 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 32
- 239000000376 reactant Substances 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- SBYHFKPVCBCYGV-UHFFFAOYSA-N quinuclidine Chemical compound C1CC2CCN1CC2 SBYHFKPVCBCYGV-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 12
- QVCUKHQDEZNNOC-UHFFFAOYSA-N 1,2-diazabicyclo[2.2.2]octane Chemical compound C1CC2CCN1NC2 QVCUKHQDEZNNOC-UHFFFAOYSA-N 0.000 abstract 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- -1 SDA cations Chemical class 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 241000408939 Atalopedes campestris Species 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 150000001399 aluminium compounds Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C01B39/026—After-treatment
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
公开了一种使用N,N'‑二甲基‑1,4‑二氮杂双环[2.2.2]辛烷二价阳离子作为结构导向剂制备LEV骨架类型沸石的方法。
Description
相关申请的交叉引用
本申请要求2015年8月20日提交的美国临时申请No.62/207,454的优先权,其通过引用并入本文。
技术领域
本公开一般涉及使用N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子作为结构导向剂制备LEV骨架类型沸石的方法。
背景技术
分子筛由国际沸石协会的结构委员会根据IUPAC委员会关于沸石命名法的规则分类。根据这种分类,骨架类型沸石和其他已被确定结构的结晶微孔分子筛被指定三字母代码,并描述在“Atlas of Zeolite Framework Types”,第六修订版,Elsevier(2007)中。
其结构已经确定的一种已知分子筛是命名为LEV的材料,该材料是以具有十七面孔隙为特征的分子筛,由此LEV骨架类型沸石获得它们的大的微孔体积(约0.3cm3/g),尽管该结构仅具有小的8元环(8MR)孔开口。由于其独特的结构,LEV骨架类型沸石作为用于甲醇-烯烃(MTO)转化和NOx还原的催化剂具有重要意义。LEV骨架类型材料的实例包括levyne、AlPO-35、CoDAF-4、LZ-132、NU-3、RUB-1、SAPO-35、ZK-20和ZnAPO-35。
通常使用外来有机模板作为结构导向剂(如基于奎宁环基的模板)来制备合成LEV骨架类型沸石。LEV骨架类型沸石的商业开发受到其合成所需的结构导向剂的复杂性的阻碍,因此对于找到用于合成硅铝酸盐LEV骨架类型沸石(特别是具有的SiO2/Al2O3摩尔比适用于MTO转化和NOx还原应用的材料)的替代结构导向剂有着很大的兴趣。
现在已经发现,可以使用N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子作为结构导向剂制备SiO2/Al2O3摩尔比为10-55的LEV骨架类型沸石。这种阳离子种类可以从市场上可买到的原料方便而廉价地制备。
发明概要
在一个方面,提供了制备LEV骨架类型沸石的方法,所述方法通过在结晶条件下接触:(1)至少一种氧化硅源;(2)至少一种氧化铝源;(3)至少一种选自周期表第1族和第2族的元素的源;(4)N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子;和(5)氢氧根离子。
在另一方面,提供了制备LEV骨架类型沸石的方法,通过:(a)制备反应混合物,所述反应混合物含有:(1)至少一种氧化硅源;(2)至少一种氧化铝源;(3)至少一种选自周期表第1族和第2族的元素的源;(4)N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子;(5)氢氧根离子;和(6)水;和(b)使所述反应混合物经受足以形成所述LEV骨架类型沸石的晶体的结晶条件。
在一方面,提供了在其孔结构内含有N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子的硅铝酸盐LEV骨架类型沸石。
在一方面,提供了结晶LEV骨架类型沸石,所述LEV骨架类型沸石在合成后原样且在无水状态下具有以摩尔比计的如下组成:
宽泛的 | 典型值 | |
SiO2/Al2O3 | 10至55 | 15至40 |
Q/SiO2 | 0.02至0.20 | 0.05至0.20 |
M/SiO2 | 0.01至0.20 | 0.02至0.15 |
其中Q代表N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子,M选自周期表第1族和第2族的元素。
附图简介
图1是实施例1中制备的合成后原样的沸石的粉末X射线衍射图(XRD)。
图2是实施例1中制备的合成后原样的沸石的扫描电子显微镜(SEM)图像。
详细说明
除非另有说明,以下术语将在整个说明书中使用并具有以下含义。
术语“沸石”是指多孔的结晶硅铝酸盐组合物,其由角共享AlO2和SiO2四面体形成。
术语“骨架类型”以在“Atlas of Zeolite Framework Types”,第六修订版,Elsevier,2007中描述的含义使用。
如本文所使用的,元素周期表族的编号方案如Chem.Eng.News,63(5),26-27(1985)所公开的那样。
在制备LEV骨架类型沸石时,使用N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子作为结构导向剂(“SDA”),也称为结晶模板。用于制造LEV骨架类型沸石的SDA由以下结构(1)表示:
N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子
SDA阳离子与阴离子结合,阴离子可以是对沸石形成无害的任何阴离子。代表性的阴离子包括周期表第17族的元素(例如氟离子、氯离子、溴离子和碘离子)、氢氧根、硫酸根、四氟硼酸根、乙酸根、羧酸根等。
反应混合物
通常,硅铝酸盐LEV骨架类型沸石通过以下步骤制备:(a)制备反应混合物,所述反应混合物含有:(1)至少一种氧化硅源;(2)至少一种氧化铝源;(3)至少一种选自周期表第1族和第2族的元素的源;(4)N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子;(5)氢氧根离子;和(6)水;和(b)使所述反应混合物经受足以形成所述LEV骨架类型沸石的晶体的结晶条件。
形成沸石的反应混合物以摩尔比计的组成在下表1所示:
表1
宽泛的 | 典型值 | |
SiO2/Al2O3 | 10至100 | 15至60 |
M/SiO2 | 0.05至0.80 | 0.10至0.45 |
Q/SiO2 | 0.10至0.80 | 0.15至0.30 |
OH/SiO2 | 0.20至1.00 | 0.20至0.60 |
H2O/SiO2 | 10至50 | 15至50 |
其中组成变量M和Q如上所述。
本文中可用于氧化硅的来源包括热解法二氧化硅、沉淀硅酸盐、二氧化硅水凝胶、硅酸、胶态二氧化硅、原硅酸四烷基酯(例如原硅酸四乙酯)和二氧化硅氢氧化物。
本文可用于氧化铝的来源包括铝酸盐、氧化铝和铝化合物(例如氯化铝、氢氧化铝和硫酸铝)、高岭土和其它沸石(例如沸石Y)。
如上文所述,对于本文所述的每个实施方案,反应混合物可以使用选自元素周期表第1和2族的至少一种元素(本文称为M)的源形成。在一个子实施方案中,反应混合物使用元素周期表第1族的元素的源形成。在另一个子实施方案中,使用钠(Na)源形成反应混合物。任何不会对结晶过程有害的含M化合物都是合适的。这样的1族和2族元素的源包括其氧化物,氢氧化物,硝酸盐,硫酸盐,卤化物,乙酸盐,草酸盐和柠檬酸盐。
任选地,反应混合物可以含有晶种。在一个实施方案中,结晶沸石的合成通过存在基于反应混合物总重量0.05-10.0重量%(例如,1-5重量%)的晶种而促进。晶种可以与所需的沸石同构,例如先前合成的产物。
对于本文所述的每个实施方案,反应混合物可以由多于一种来源供应。而且,两种或更多种反应组分可以由一种来源提供。
反应混合物可以分批或连续制备。本文所述的结晶沸石的晶体尺寸、形态和结晶时间可以随着反应混合物的性质和结晶条件而变化。
结晶和合成后处理
本文描述的LEV骨架类型沸石的结晶可以在静态、翻转或搅拌条件下在合适的反应容器如聚丙烯罐或特氟隆衬里或不锈钢高压釜中在125℃至200℃下足够的时间(例如1天至28天)在所使用的温度下发生结晶。
一旦形成沸石晶体,通过标准机械分离技术如离心或过滤将固体产物与反应混合物分离。将晶体水洗,然后干燥,得到合成后原样的沸石晶体。干燥步骤通常在低于200℃的温度下进行。
作为结晶过程的结果,回收的结晶沸石产物在其孔内含有用于合成的至少一部分结构导向剂。
通常在使用前通过煅烧将结构导向剂从沸石中至少部分除去。煅烧主要包括在含氧气体存在下,任选在蒸汽存在下,将含有结构导向剂的沸石在200℃至800℃的温度下加热。结构导向剂也可以通过如美国专利第6,960,327号中所述的光解技术除去。
根据所需的程度和取决于沸石的组成,可以根据本领域公知的技术通过与其它阳离子的离子交换来替换合成后原样或煅烧后的沸石中的任何阳离子。优选的取代阳离子包括金属离子、氢离子、氢前体,例如铵离子及其混合物。特别优选的阳离子是为某些化学转化反应定制催化活性的阳离子。这些包括氢、稀土金属和元素周期表第2至15族的金属。如本文所用,术语“合成后原样”是指沸石在结晶之后、去除SDA阳离子之前的其形式。
可以将本文公开的沸石与其它材料(例如粘合剂和/或基质材料)结合配制成催化剂组合物,所述其它材料例如粘合剂和/或基质材料为最终催化剂提供额外的硬度或催化活性。
沸石的表征
通过本文公开的方法制备的LEV骨架类型沸石在合成后原样且在无水状态下具有下表2所述的组成(以摩尔比计)
表2
宽泛的 | 典型值 | |
SiO2/Al2O3 | 10至55 | 15至40 |
Q/SiO2 | 0.02至0.20 | 0.05至0.20 |
M/SiO2 | 0.01至0.20 | 0.02至0.15 |
其中组成变量M和Q如上所述。
应该注意的是,合成后原样形式的LEV骨架类型沸石可以具有与用于制备合成后原样形式的反应混合物的反应物的摩尔比不同的摩尔比。该结果可能发生是由于不完全引入100%的反应物到(所述反应混合物)形成的晶体中。
通过本文描述的方法合成的LEV骨架类型沸石的特征在于它们的X射线衍射图。代表LEV骨架类型沸石的X射线衍射图可以参见“Collection of Simulated XRD PowderPatterns for Zeolites”第五修订版,Elsevier,2007。在X射线衍射图中的微小变化归因于晶格常数的改变,可能由特定样品的骨架种类的摩尔比的变化造成。此外,足够小的晶体将影响峰的形状和强度,导致显著的峰加宽。在衍射图中的微小变化可以由制备过程中使用的有机化合物的变化而造成。煅烧也可导致在X射线衍射图中微小偏移。尽管有这些微小的扰动,但基本晶格结构保持不变。
通过标准技术收集本文所示的粉末X射线衍射图。辐射为CuKα辐射。从峰的相对强度读取作为2θ(其中θ是布拉格角)的函数的峰高度和位置,并且可计算出与记录线相对应的面间距d。
实施例
以下说明性实施例旨在是非限制性的。
实施例1
将1.30克去离子水、4.70克硅酸钠溶液(Sigma-Aldrich)和5.95克19%的N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷(N,N’-dimethyl-1,4-diazabycyclo[2.2.2]octane)氢氧化物溶液(Sachem)在特氟龙内衬中混合在一起。然后,将1.00g LZ-210Y-沸石粉末加入到溶液中。搅拌所得到的凝胶直至变成均相。然后将衬里容器加盖并放在Parr钢高压釜反应器中。将高压釜放在烘箱中并在135℃加热4天。通过离心从冷却的反应器中回收固体产物,用去离子水洗涤并在95℃下干燥。
通过粉末XRD和SEM分析所得产物。图1所示的粉末XRD图表明该材料是纯LEV骨架类型沸石。图2所示的SEM图像表明均匀的晶体场。
通过ICP元素分析测定,产物的SiO2/Al2O3摩尔比为14.6。
实施例2
将4.03克去离子水、19.32克硅酸钠溶液(Sigma-Aldr ich)和22.33克19%的N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷(N,N’-dimethyl-1,4-diazabycyclo[2.2.2]octane)氢氧化物溶液(SACHEM Inc)在特氟龙内衬中混合在一起。然后,将3.00g LZ-210Y-沸石粉末加入到溶液中。搅拌所得到的凝胶直至变成均相。然后将衬里容器加盖并放在Parr钢高压釜反应器中。将高压釜放在烘箱中并在150℃加热3天。通过离心从冷却的反应器中回收固体产物,用去离子水洗涤并在95℃下干燥。
通过粉末XRD和SEM分析所得产物为纯LEV骨架类型沸石。
通过ICP元素分析测定,产物的SiO2/Al2O3摩尔比为17.4。
实施例3
将14.10克硅酸钠溶液(Sigma-Aldrich)和26.80克的19%的N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷(N,N’-dimethyl-1,4-diazabycyclo[2.2.2]octane)氢氧化物溶液(Sachem)在特氟龙内衬中混合在一起。然后,将3.00克CBV720Y-沸石粉末(ZeolystInternational,SiO2/Al2O3摩尔比=30)加入到溶液中。搅拌所得到的凝胶直至变成均相。然后将衬里容器加盖并放在Parr钢高压釜反应器中。将高压釜放在烘箱中并在150℃加热3天。通过离心从冷却的反应器中回收固体产物,用去离子水洗涤并在95℃下干燥。
通过粉末XRD和SEM分析所得产物为纯LEV骨架类型沸石。
通过ICP元素分析测定,产物的SiO2/Al2O3摩尔比为18.6。
实施例4
将实施例1的合成后原样的沸石产物在马弗炉内在空气流下以1℃/分钟的速率加热至540℃下煅烧,并在540℃下保持5小时,冷却,然后通过粉末XRD分析。粉末XRD图谱表明,在煅烧除去有机SDA后,材料保持稳定。
实施例5
使用N2作为吸附物并通过BET法对来自实施例4的煅烧产物进行微孔体积分析。沸石表现出相当大的空隙体积,其微孔体积为0.25cm3/g。
实施例6
甲醇转化
将铵交换产物以5kps i造粒,粉碎并过筛至20-40目。将0.20g催化剂(用刚玉按4:1v/v稀释)置于分流管式炉中的不锈钢下流式反应器中。催化剂在400℃下在流动氮气下原位预热。以1.3h–1WHSV的速度将含10%甲醇的氮气进料引入反应器中。
使用塞流和具有FID检测器的Agi lent在线气相色谱仪收集反应数据。在HP-PLOTQ柱上不同时间分析反应产物。结果总结在表3中。
表3
表3中所示的产物,在甲醇催化转化为主要是C2-C4范围烯烃的反应中的产物形状选择性方面,与小孔沸石的那些一致。没有观察到芳香族产物。
如本文所使用的,术语“包含”意味着包括在该术语之后被识别的元素或步骤,但是任何这样的元素或步骤不是穷尽的,并且实施例可以包括其他元素或步骤。
除非另外指明,元素、物质或其他组分的列举,可以选择单个组分或混合组分,旨在包括所列举的组分及其混合物的所有可能的亚属组合。
本申请中引用的所有文件在此以其全部内容通过引用并入本文,只要这样的公开内容不与本文不一致。
Claims (8)
1.一种制备LEV骨架类型沸石的方法,包括:
(a)制备反应混合物,所述反应混合物含有:
(1)至少一种氧化硅源;
(2)至少一种氧化铝源;
(3)至少一种选自周期表第1族和第2族的元素(M)的源;
(4)N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子(Q);
(5)氢氧根离子;和
(6)水;和
(b)使所述反应混合物经受足以形成所述沸石的晶体的结晶条件。
2.根据权利要求1所述的方法,其中所述沸石由反应混合物制备,所述反应混合物包含以摩尔比计的以下组分:
3.根据权利要求1所述的方法,其中所述沸石由反应物制备,所述反应物包含以摩尔比计的以下组分:
4.根据权利要求1所述的方法,其中所述沸石在合成后原样且在无水状态下具有以摩尔比计的如下组成:
5.根据权利要求1所述的方法,其中所述沸石在合成后原样且在无水状态下具有以摩尔比计的如下组成:
6.一种硅铝酸盐LEV骨架类型沸石,所述沸石在其孔结构内包含N,N'-二甲基-1,4-二氮杂双环[2.2.2]辛烷二价阳离子。
7.根据权利要求6所述的沸石,其中所述沸石的SiO2/Al2O3摩尔比为10至55。
8.根据权利要求6所述的沸石,其中所述沸石的SiO2/Al2O3摩尔比为15至40。
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WO2017030618A1 (en) | 2017-02-23 |
KR20180042227A (ko) | 2018-04-25 |
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