CN111051243A - 分子筛ssz-110、其合成和用途 - Google Patents
分子筛ssz-110、其合成和用途 Download PDFInfo
- Publication number
- CN111051243A CN111051243A CN201980004051.2A CN201980004051A CN111051243A CN 111051243 A CN111051243 A CN 111051243A CN 201980004051 A CN201980004051 A CN 201980004051A CN 111051243 A CN111051243 A CN 111051243A
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- CN
- China
- Prior art keywords
- molecular sieve
- sio
- imidazole
- bis
- dimethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 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 63
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 62
- 238000003786 synthesis reaction Methods 0.000 title description 11
- 230000015572 biosynthetic process Effects 0.000 title description 10
- 238000000034 method Methods 0.000 claims abstract description 31
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 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 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 20
- YUHYOFOYFVGEMY-UHFFFAOYSA-N 2,3-dimethyl-1,2-dihydroimidazole Chemical compound CC1NC=CN1C YUHYOFOYFVGEMY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 17
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 17
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 9
- 239000001273 butane Substances 0.000 claims abstract description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims abstract description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 60
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- 229910052681 coesite Inorganic materials 0.000 claims description 22
- 229910052906 cristobalite Inorganic materials 0.000 claims description 22
- 229910052682 stishovite Inorganic materials 0.000 claims description 22
- 229910052905 tridymite Inorganic materials 0.000 claims description 22
- 239000011541 reaction mixture Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001868 water Inorganic materials 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 7
- -1 (2, 3-dimethyl-1H-imidazole) Butane Chemical compound 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
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- 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 5
- 239000001307 helium Substances 0.000 description 4
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- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
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- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000003039 volatile agent Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- OMIVCRYZSXDGAB-UHFFFAOYSA-N 1,4-butanediyl Chemical group [CH2]CC[CH2] OMIVCRYZSXDGAB-UHFFFAOYSA-N 0.000 description 1
- SXHJWZUJZTYMRP-UHFFFAOYSA-N 1-[4-(2,3-dimethyl-1,2-dihydroimidazol-1-ium-1-yl)butyl]-2,3-dimethyl-1,2-dihydroimidazol-1-ium dihydroxide Chemical compound [OH-].[OH-].C(CCC[NH+]1C(N(C=C1)C)C)[NH+]1C(N(C=C1)C)C SXHJWZUJZTYMRP-UHFFFAOYSA-N 0.000 description 1
- HLZYHEWIIQQUFY-UHFFFAOYSA-N 2-ethyl-1,3,4-trimethyl-2h-imidazole Chemical compound CCC1N(C)C=C(C)N1C HLZYHEWIIQQUFY-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical group O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
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- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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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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Abstract
Description
相关申请的交叉引用
本申请要求2018年1月24日提交的美国临时申请系列号62/621116的优先权和权益。
领域
本公开内容涉及一种新的STW骨架类型的合成铝硅酸盐分子筛(称作SSZ-110),其合成以及其在有机化合物转化反应和吸附过程中的用途。
背景
已知沸石材料具有作为吸附剂材料的使用性和具有用于各种类型的有机转化反应的催化性能。某些沸石材料是有序的、多孔结晶材料,其具有通过X射线衍射所测定的确定的晶体结构。在沸石材料内,存在着大量较小的腔室,所述腔室可以通过许多更小的通道或孔来互连。由于这些孔的尺寸达到容许吸附某些尺寸的分子同时拒绝更大尺寸的那些的程度,因此这些材料已被称作“分子筛”并且以多种方式使用以利用这些性能。
分子筛由国际沸石协会的结构委员会根据IUPAC沸石命名委员会的规则来分类。根据该分类,骨架类型沸石和其他结晶微孔分子筛(对于其来说结构已经是公认的)被赋予三字母代码,并且描述在“Atlas of Zeolite Framework Types”,第六修订版,Elsevier(2007)中。
由国际沸石协会鉴定为具有骨架类型STW的分子筛是已知的。锗硅酸盐沸石SU-32是一种已知的使用二异丙基胺作为结构导向剂的结晶STW材料(参见L.Tang等,NatureMater.2008,7,381-385)。SU-32含有10元环手性螺旋通道,这些通道通过直的8元环通道以不同水平相交。
A.Rojas等(Angew.Chem.Int.Ed.2012,51,3854-3856)公开了一种STW骨架类型的纯二氧化硅手性沸石HPM-1,及其使用2-乙基-1,3,4-三甲基咪唑阳离子作为结构导向剂的合成。
N.Zhang等(J.Solid State Chem.2015,225,271-277)公开了使用N,N-二乙基乙二胺作为结构导向剂合成纯STW类型锗硅酸盐以及Cu取代和Co取代的STW-类沸石(zeotype)材料。
对于催化应用来说,引入催化活性位点如铝原子对于为分子筛赋予酸性性能来说是重要的。
因此,提供一种新的STW骨架类型的铝硅酸盐分子筛,本文中称作SSZ-110,其具有小于100的SiO2/Al2O3摩尔比。分子筛SSZ-110可以使用本文中公开的有机结构导向剂来合成。
概述
在一方面,提供一种新的STW骨架类型的铝硅酸盐分子筛,其具有小于100的SiO2/Al2O3的摩尔比。
在另一方面,提供一种合成STW骨架类型的铝硅酸盐分子筛的方法,该方法包括:(a)提供反应混合物,其包含:(1)氧化硅源;(2)氧化铝源;(3)有机结构导向剂(Q),其包含1,4-双(2,3-二甲基-1H-咪唑)丁烷双阳离子、1,5-双(2,3-二甲基-1H-咪唑)戊烷双阳离子和1,6-双(2,3-二甲基-1H-咪唑)己烷双阳离子中的一种或多种;(4)氟离子源;以及(5)水;和(b)使所述反应混合物经历足以形成铝硅酸盐分子筛晶体的结晶条件。
在另一方面,提供一种STW骨架类型的铝硅酸盐分子筛,以其合成后原样的形式在其孔中包含1,4-双(2,3-二甲基-1H-咪唑)丁烷双阳离子、1,5-双(2,3-二甲基-1H-咪唑)戊烷双阳离子和1,6-双(2,3-二甲基-1H-咪唑)己烷双阳离子中的一种或多种。
在又另一方面,提供一种将包含有机化合物的原料转化成转化产物的方法,所述方法包括使所述原料在有机化合物转化条件下与催化剂接触,所述催化剂包含本文所述的铝硅酸盐分子筛的活性形式。
附图说明
图1是实施例2中制备的合成后原样的分子筛的粉末X射线衍射(XRD)图案。
详细描述
引言
术语“铝硅酸盐”指的是在其骨架内包括硅和铝氧化物的分子筛组成。在一些情况下,这些氧化物中的任一可以任选地用其他氧化物取代。“纯铝硅酸盐”是在骨架中具有不可测出的其他金属氧化物的那些分子筛结构。当描述为“任选取代的”时,相应的骨架可以含有硼、镓、铟、锗、锡、钛、铁或其他取代一个或多个尚未包含在母体骨架中的原子的原子。
术语“骨架类型”以“Atlas of Zeolite Framework Types”,第六修订版,Elsevier(2007)中所述含义来使用。
术语“合成后原样的”在本文中用于指的是分子筛处于其结晶后、除去有机结构导向剂之前的形式。
术语“无水”在本文中用于指的是分子筛基本上没有物理吸附和化学吸附的水二者。
如本文所用,周期表族的编号方案如Chem.Eng.News 1985,63(5),26-27中所公开。
SiO2/Al2O3摩尔比(SAR)在本文中通过电感耦合等离子体–质谱法(ICP-MS)测定。
“表面积”在本文中通过在其沸点下的N2吸附来测定。B.E.T.表面积通过5点法在P/P0=0.050、0.088、0.125、0.163和0.200计算。样品首先在流动的干燥N2存在下在400℃下预处理6小时以消除任何吸附的挥发物如水或有机物。
“微孔体积”在本文中通过在其沸点下的N2吸附来测定。微孔体积通过t-图法在P/P0=0.050、0.088、0.125、0.163和0.200测定。样品首先在流动的干燥N2存在下在400℃下预处理6小时以消除任何吸附的挥发物如水或有机物。
“布朗斯台德酸度”在本文中通过异丙胺-温度-程序化解吸(IPam TPD)来测定,该异丙胺-温度-程序化解吸(IPam TPD)改编自由T.J.Gricus Kofke等(J.Catal.1988,114,34-45),T.J.Gricus Kofke等(J.Catal.1989,115,265-272)和J.G.Tittensor等(J.Catal.1992,138,714-720)所公开的描述。样品在流动的干燥H2中在400℃-500℃下预处理1小时。脱水的样品然后在流动的干燥氦气中冷却到120℃,并且在用异丙胺饱和的流动氦气中在120℃下保持30分钟以用于吸附。异丙胺饱和的样品然后在流动的干燥氦气中以10℃/min的速率加热直到500℃。布朗斯台德酸度基于通过热重分析(TGA)的重量损失相对于温度和通过质谱的流出物NH3和丙烯来计算。
“约束指数”(CI)在本文中根据由S.I.Zones等(Micropor.Mesopor.Mater.2000,35-36,31-46)所述的方法来测定。该测试设计成允许在由8、10和≥12元环(MR,构成环的四面体或氧原子的数目)孔组成的孔体系之间进行区分。CI值随分子筛的孔尺寸的增加而降低。例如沸石经常基于如下的CI值来分类:对于大孔(12-MR)或超大孔(≥14-MR)分子筛来说CI<1;对于中孔(10-MR)分子筛来说1≤CI≤12;对于小孔(8-MR)分子筛来说CI>12。
反应混合物
通常,STW骨架类型的铝硅酸盐分子筛可以通过如下方式来合成:(a)提供反应混合物,其包含:(1)氧化硅源;(2)氧化铝源;(3)有机结构导向剂(Q),其包含1,4-双(2,3-二甲基-1H-咪唑)丁烷双阳离子、1,5-双(2,3-二甲基-1H-咪唑)戊烷双阳离子和1,6-双(2,3-二甲基-1H-咪唑)己烷双阳离子中的一种或多种;(4)氟离子源;以及(5)水;和(b)将所述反应混合物经历足以形成铝硅酸盐分子筛晶体的结晶条件。
所述反应混合物可以具有在以下表1中所述范围内的以摩尔比计的组成:
表1
反应物 | 有用的 | 示例性 |
SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> | 20至<100 | 20-80 |
Q/SiO<sub>2</sub> | 0.20-0.75 | 0.25-0.65 |
F/SiO<sub>2</sub> | 0.20-0.75 | 0.25-0.65 |
H<sub>2</sub>O/SiO<sub>2</sub> | 2-100 | 4-40 |
其中Q如以上本文中所述。
合适的氧化硅源包括胶体二氧化硅、热解法二氧化硅(fumed silicas)、沉淀二氧化硅、碱金属硅酸盐和正硅酸四烷基酯。
合适的氧化铝源包括水合氧化铝和水溶性铝盐(例如硝酸铝)。
氧化硅和氧化铝的组合源可以另外地或可替代地使用,并且可以包括铝硅酸盐沸石(例如沸石Y)和粘土或经处理的粘土(例如变高岭土)。
合适的氟离子源包括氢氟酸、氟化铵和二氟化氢铵。
有机结构导向剂(Q)包含分别由以下结构(1)-(3)表示的1,4-双(2,3-二甲基-1H-咪唑)丁烷双阳离子、1,5-双(2,3-二甲基-1H-咪唑)戊烷双阳离子和1,6-双(2,3-二甲基-1H-咪唑)己烷双阳离子中的一种或多种:
合适的Q源是相关的二季铵化合物的氢氧化物和/或其他盐。
所述反应混合物还可以理想地以反应混合物的0.01-10000ppm重量(例如100-5000ppm重量)的量含有分子筛材料的晶种,例如来自在先合成的SSZ-110。种晶在降低发生完全结晶所需的时间量方面可以是有利的。另外,种晶可导致通过促进在任何不期望相上的SSZ-110的成核和/或形成所获得的产物的纯度增加。
对于本文所述的每个实施方案,所述反应混合物可以通过大于一种源来提供。同样,两种或更多种反应组分可以通过一种源来提供。
所述反应混合物可以分批或连续制备。本文中分子筛的晶体尺寸、形态和结晶时间可以随反应混合物的性质和结晶条件而变化。
结晶和合成后处理
分子筛从以上反应混合物中结晶可以在静态、翻滚或搅拌条件下,在合适的反应器容器如聚丙烯罐或特氟隆衬里的或不锈钢高压釜中,在125℃-200℃的温度下进行足以在所用温度下发生结晶的时间如5-40天。结晶通常在高压釜中进行,以使得反应混合物经历自生的压力。
一旦分子筛晶体已经形成,则固体产物通过标准机械分离技术如离心分离或过滤而从反应混合物中回收。将回收的晶体进行水洗涤,和然后干燥以获得合成后原样的分子筛晶体。干燥步骤典型地在小于200℃的温度下进行。
作为结晶过程的结果,回收的结晶产物在其孔结构内含有合成中所用的有机结构导向剂的至少一部分。
以其合成后原样且无水形式,分子筛SSZ-110可以具有包含以下表2中所述摩尔关系的化学组成:
表2
最宽的 | 示例性 | |
SiO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> | <100 | 20-80 |
Q/SiO<sub>2</sub> | >0至0.1 | >0至0.1 |
F/SiO<sub>2</sub> | >0至0.1 | >0至0.1 |
其中Q如以上本文中上所述。
由于它们在结晶期间存在而与合成后原样的材料相关的Q和F组分通过常规结晶后方法而容易地除去。
合成后原样的分子筛可以进行处理以除去其合成中所用的有机结构导向剂的部分或全部。这可以通过热处理来方便地进行,在该热处理中将合成后原样的材料在至少约370℃的温度下加热至少1分钟和通常不长于20小时。热处理可以在至多925℃的温度下进行。尽管低于大气压可以用于热处理,但是出于方便的原因,大气压是期望的。另外地或可替代地,有机结构导向剂可以通过用臭氧处理来除去(参见例如A.N.Parikh等,Micropor.Mesopor.Mater.2004,76,17-22)。贫有机物的产物(特别是为其金属、氢和铵形式)在某些有机物(例如烃)转化反应的催化方面是特别有用的。在本公开内容中,为其氢形式的贫有机物的分子筛被称作具有或不具有金属功能存在的分子筛的“活性形式”。
本发明分子筛的合成可以在不存在第1或2族金属阳离子的情形下完成,由此消除了对于处理后对产物进行离子交换以除去任何包藏的有机结构导向剂的需要。但是,取决于材料的SiO2/Al2O3摩尔比,分子筛中的任何阳离子可以根据本领域公知的技术(例如通过与其他阳离子进行离子交换)来置换。优选的置换阳离子可以包括金属离子、氢离子、氢前体(例如铵)离子及其混合物。特别优选的置换阳离子可以包括针对某些有机化合物转化反应定制催化活性的那些(例如氢、稀土金属、和/或元素周期表第2-15族的一种或多种金属)。
以其煅烧形式,分子筛SSZ-110可以具有包含以下摩尔关系的化学组成:
Al2O3:(n)SiO2
其中n<100(例如20至<100,20-95,20-90,20-85,20-80,20-75,20-70,20-65,20-60,25至<100,25-95,25-90,25-85,25-80,25-75,25-70,25-65,25-60,30至<100,30-95,30-90,30-85,30-80,30-75,30-70,30-65,30-60,35至<100,35-95,35-90,35-85,35-80,35-75,35-70,35-65,35-60,40至<100,40-95,40-90,40-85,40-80,40-75,40-70,40-65,或40-60)。
吸附和催化
分子筛SSZ-110可以用作吸附剂或用作催化剂以催化多种有机化合物转化过程,包括许多具有目前商业/工业重要性的过程。通过SSZ-110本身或其与一种或多种其他催化活性物质(包括其他结晶催化剂)组合来有效催化的化学转化过程的实例包括需要具有酸活性的催化剂的那些。可以通过SSZ-110催化的有机转化过程的实例包括烷基化、(加氢)裂化、歧化、异构化和低聚。其他有机转化过程可以包括醇与烯烃的反应和有机含氧化合物转化成烃。
如在有机化合物(例如烃)转化过程中所用的许多催化剂的情况下那样,可以令人期望的是引入SSZ-110和对有机转化过程中所用的温度和其他条件耐受的另一材料。这样的材料可以包括活性和非活性材料以及合成或天然存在的沸石,以及无机材料如粘土、二氧化硅、和/或金属氧化物如氧化铝。后者可以是天然存在的或呈凝胶状沉淀物或凝胶的形式,包括二氧化硅和金属氧化物的混合物。与本发明分子筛结合地(即与本发明分子筛组合和/或在合成分子筛期间存在)使用活性材料可倾向于改变某些有机转化过程中催化剂的转化和/或选择性。非活性材料可以合适地充当稀释剂以控制在给定过程中的转化量,以使得产物可以以经济和有序方式获得,而无需使用其他(更昂贵)的手段来控制反应速率。这些材料可以引入天然存在的粘土(例如膨润土和高岭土)中以改进催化剂在商业运行条件下的抗碎强度。这些材料(即粘土,氧化物等)可以充当催化剂的粘结剂。可以令人期望的是提供具有良好抗碎强度的催化剂,因为在商业用途中,可以令人期望的是防止催化剂破裂成粉末状材料(磨损)。这些粘土和/或氧化物粘结剂通常仅出于改进催化剂的抗碎强度的目的而采用。
可以与SSZ-110复合的天然存在的粘土可以包括蒙脱石和高岭土族,所述族包括亚膨润土(sub-bentonite)和通常称为Dixie、McNamee、Georgia和Florida粘土的高岭土或其中主要矿物成分为埃洛石、高岭石、迪开石、珍珠陶土或蠕陶土的其他那些。这样的粘土可以以如原始开采那样的原状态使用,或最初经历煅烧、酸处理或化学改性。可用于与本发明分子筛复合的粘结剂可以另外地或可替代地包括无机氧化物如二氧化硅、氧化锆、二氧化钛、氧化镁、氧化铍、氧化铝及其混合物。
可替代地或除了前述材料之外,SSZ-110可以与多孔基质材料复合,该多孔基质材料例如二氧化硅-氧化铝、二氧化硅-氧化镁、二氧化硅-氧化锆、二氧化硅-氧化钍、二氧化硅-氧化铍、二氧化硅-二氧化钛,和/或一种或多种三元组合物如二氧化硅-氧化铝-氧化钍、二氧化硅-氧化铝-氧化锆、二氧化硅-氧化铝-氧化镁和二氧化硅-氧化镁-氧化锆。
分子筛SSZ-110和无机氧化物基质的相对比例可以宽泛变化,并且SSZ-110含量是复合材料的1-90wt%(例如2-80wt%)。
实施例
以下的示例性实施例旨在是非限定性的。
实施例1
配衡的特氟隆杯装有1,1’-(1,4-丁二基)双[2,3-二甲基-1H-咪唑]二氢氧化物(2.5mmol的氢氧化物当量)。然后,加入1.04g的正硅酸四乙酯(5mmol的SiO2)和作为氧化铝源的0.02g的Reheis F-2000以提供50的起始SiO2/Al2O3摩尔比。然后将来自在先合成的SSZ-110晶种(10mg)加入混合物中。将特氟隆杯保持封闭2天,和然后打开所述杯以开始一些水和乙醇从正硅酸四乙酯中的蒸发。当发现固含量是1.09g时,然后将50%HF溶液(0.09g)加入至反应混合物中。将特氟隆杯盖上盖子,并且置于Parr钢高压釜反应器内。将该高压釜置于烘箱中,并且在170℃下在旋转(43rpm)下加热2周。固体产物通过过滤从冷却的反应器中回收,用去离子水洗涤并且在95℃下干燥。
合成后原样的产物的粉末XRD与作为STW拓扑的分子筛的材料一致。
化学分析显示合成后原样的产物的铝含量是1.6wt%,氟化物含量是0.47wt%,和SiO2/Al2O3摩尔比是49。
实施例2
配衡的特氟隆杯装有0.90g的CBV-780Y沸石粉末(Zeolyst International;SiO2/Al2O3摩尔比=80)和7.5mmol的1,1’-(1,4-丁二基)双[2,3-二甲基-1H-咪唑]二氢氧化物。将混合物置于通风厨中,并且水含量通过经过若干天的蒸发来降低以实现目标H2O/SiO2摩尔比为7。然后,逐滴加入7.5mmol的50%HF溶液。将衬里盖上盖子,并且置于Parr钢高压釜反应器中。将该高压釜置于烘箱中,并且在160℃下在旋转(43rpm)下加热7天。固体产物通过过滤从冷却的反应器中回收,用去离子水洗涤并且在95℃下干燥。
所形成的合成后原样的产物通过粉末XRD来分析。图1中的粉末X射线衍射图案与作为STW骨架类型的分子筛的产物一致。
将实施例2的合成后原样的分子筛产物在马弗炉内部在2%氧气/98%氮气流下以1℃/min的速率加热到595℃煅烧,并且在595℃下保持5小时和冷却到环境温度。
粉末XRD图案指示所述材料在煅烧以除去结构导向剂后保持稳定。
煅烧的分子筛的物理性能汇总在表3中。
表3
微孔体积 | 0.0829cm<sup>3</sup>/g |
B.E.T.表面积 | 206.48m<sup>2</sup>/g |
布朗斯台德酸度 | 279μmol/g |
实施例4
约束指数测定
将实施例2的煅烧的分子筛在4-5kpsi下粒化,并且压碎和过筛至20-40。然后,将0.50g分子筛填充到3/8英寸不锈钢管中,在分子筛床的两侧上都具有铝氧粉。使用Lindburg炉来加热反应器管。以10mL/min和在大气压下将氦气引入反应器管中。将反应器加热到约371℃和将50/50(w/w)的正己烷和3-甲基戊烷进料以8μL/min的速率引入反应器中。进料递送经由Brownlee泵来进行。在进料引入15分钟后,开始直接取样到气相色谱仪(GC)中。
约束指数值(不包括2-甲基戊烷)使用本领域已知的方法从GC数据来计算,并且发现对于15-225分钟的在线时间来说是2.25-2.96,其是10元环分子筛的特征。
Claims (13)
1.一种STW骨架类型的铝硅酸盐分子筛,其具有小于100的SiO2/Al2O3摩尔比。
2.权利要求1的铝硅酸盐分子筛,其中所述SiO2/Al2O3摩尔比是20-80。
4.权利要求3的方法,其中所述反应混合物具有以摩尔比计的如下组成:
。
5.权利要求3的方法,其中所述反应混合物具有以摩尔比计的如下组成:
。
6.权利要求3的方法,其中所述反应混合物进一步包含晶种。
7.权利要求6的方法,其中所述晶种以反应混合物的0.01-10000ppm重量的量存在。
8.权利要求6的方法,其中所述晶种包含STW骨架类型的分子筛。
9.权利要求3的方法,其中所述结晶条件包括125℃-200℃的温度。
11.权利要求10的铝硅酸盐分子筛,其具有小于100的SiO2/Al2O3摩尔比。
12.权利要求11的分子筛,其中所述SiO2/Al2O3的摩尔比是20-80。
13.一种将包含有机化合物的原料转化成转化产物的方法,所述方法包括使所述原料在有机化合物转化条件下与催化剂接触,所述催化剂包含权利要求1的铝硅酸盐分子筛的活性形式。
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CN102424399A (zh) * | 2011-09-05 | 2012-04-25 | 中国科学院过程工程研究所 | 一种制备硅铝磷酸盐分子筛的方法 |
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