CN1322184A - Ecr－40大孔铝磷酸盐的合成和组合物 - Google Patents
Ecr－40大孔铝磷酸盐的合成和组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000011148 porous material Substances 0.000 title abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- 150000004645 aluminates Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- -1 methyl triethanol ammonium Chemical compound 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
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- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 2
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 125000001453 quaternary ammonium group Chemical group 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 12
- 229910021536 Zeolite Inorganic materials 0.000 description 10
- 241000269350 Anura Species 0.000 description 8
- 229910017119 AlPO Inorganic materials 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 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
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000005342 ion exchange Methods 0.000 description 2
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- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- YHAPLSJUSDORPR-UHFFFAOYSA-N 2-(dimethylamino)ethane-1,1-diol Chemical compound CN(C)CC(O)O YHAPLSJUSDORPR-UHFFFAOYSA-N 0.000 description 1
- CDSLHOULXDQDPN-UHFFFAOYSA-N 2-hydroxyethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].C[NH+](C)CCO CDSLHOULXDQDPN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 239000012895 dilution Substances 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- C—CHEMISTRY; METALLURGY
- 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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/04—Aluminophosphates [APO compounds]
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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
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
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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
- C01B39/54—Phosphates, e.g. APO or SAPO compounds
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S423/00—Chemistry of inorganic compounds
- Y10S423/30—Alpo and sapo
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
本发明是一种大孔铝磷酸盐或取代铝磷酸盐,包括组合物:aR:(MxAlxPz)O2,其中R表示有机模版剂,且a=0－0.4,X=0－0.4,y=0.35－0.5,且Z=0.25－0.5,且特征在于表1的衍射图,且M可以是Si、Ga、Ge、Co、Ni、Zn、Fe、V、Ti及其组合。
Description
本发明的技术领域
本发明涉及一种新物质结晶微孔金属铝磷酸盐分子筛、其制备方法及其作为吸附剂和催化剂的应用。该物质标识为ECR-40且以水热方式由包含磷、铝、有机模版剂和金属(优选硅)的反应性源和水的凝胶制成。
本发明的背景
沸石是具有微孔三维骨架结构的结晶铝硅酸盐分子筛。一般来说，结晶沸石由角共享的AlO2和SiO2四面体组成且特征在于具有均匀尺寸的孔开口、具有显著的离子交换容量且能够可逆地解吸分散在整个晶体内部空隙的吸附相而不会明显替代构成永久晶体结构的任何原子。
沸石可在无水基础上由以下的经验结构式表示：
M2/nO∶Al2O3∶XSiO2
其中M是具有化合价n的阳离子，X一般等于或大于2。在天然生成的沸石中，M可以是Li、Na、Ca、K、Mg和Ba。M阳离子松弛键接到结构上且往往通过常规的离子交换技术完全或部分被其它阳离子替代。目前已知100种以上的天然生成和合成的沸石种类。人们注意到，尽管大多数商业专利将这些磷酸盐组合物称作“分子筛”而非沸石，但科学分类将它们归属于“沸石”(Barrer，
纯粹和应用化学，51卷，1091(1979)；Coombs等人，Canad.Mineral，35卷，1571(1997))。
其它称作沸石或分子筛且具有沸石的离子交换和/或吸附特性的结晶微孔组合物是已知的。这些物质包括铝磷酸盐和取代铝磷酸盐，例如公开于美国专利4310440和4440871。美国专利4440871公开了一类氧化硅铝磷酸盐，它被标识为首字母缩拼词SAPO且具有不同的由其X-射线衍射图确定的结构。这些结构由AlPO、SAPO、MEAPO等之后的数字来标识。(Flanigen等人，Proc.7th国际沸石会议，p.103(1986))且可包括Si、Be、Mg、Ge、Zn、Fe、Co、Ni等对Al和P的取代。本发明是首先合成具有表1所示特征X-射线衍射图的磷酸盐(AlPO/SAPO等)。
本发明的综述
本发明是一种大孔铝磷酸盐或取代铝磷酸盐，包括以下组合物：
aR：(MxAlyPz)O2
其中R表示有机模版剂，且a＝0-0.4，X＝0-0.4，y＝0.35-0.5，且Z＝0.25-0.5，且特征在于表1的衍射图，且M可以是Si、Ga、Ge、Co、Ni、Zn、Fe、V、Ti及其组合。
优选实施方案的描述
ECR-40在较简单的甲基三乙醇铵或二(二羟乙基)二甲基铵模板的存在下制成。不同于许多的这类取代磷酸盐，如八面沸石形式(AlPO/SAPO-37)，ECR-40具有高热稳定性(和在某些蒸汽下的稳定性)和对大分子(包括均三苯(misitylene))的吸附能力，可用于除加氢异构化和芳族化外的FCC和加氢裂化，其中在最后一种情况下，AlPO形式提供了用于金属催化的非酸性指数。SAPO形式能够直接合成制备低酸度催化剂而无需在合成后进行处理，这在由铝硅酸盐生产低酸度催化剂时通常是必需的。ECR-40的X-射线衍射图非常类似于以前报道的铝硅酸盐沸石ZSM-18(美国专利3950496；科学，247卷，1319页(1990))且可以是MEI结构类型的一种新组合物(沸石结构类型图集，Elsevier Press(1996)，第4版)。但ECR-40最好根据斜方晶而不是ZSM-18的特征六角单元晶胞来标引。
低酸度沸石在加氢裂化和加氢异构化之类的工艺中是需要的。大多数铝硅酸盐沸石，如FAU和β型需要进行合成后改性，将它们的酸度降至可接受值。在SAPO的情况下，酸度可通过包括在AlPO结构中的硅石掺杂剂的量来密切控制。遗憾的是，大多数大孔AlPO和SAPO具有普通的热和水热稳定性。ECR-40不具有任何这些问题在于它能够经受630℃下的模版剂烧失而不会降低结晶度，且能够在600℃的水饱和气流下经受几个小时而不会损失结晶度或吸附能力，由己烷、DBM(二甲基丁烷)、邻二甲苯和均三苯来度量。
因此，本发明包括大孔铝磷酸盐或取代铝磷酸盐，包括：
aR：(MxAlyPz)O2
其中R表示有机模版剂，且M＝0-0.4，X＝0-0.4，y＝0.35-0.5，且Z＝0.25-0.5，且特征在于图1的衍射图，该图具有表1所示的基本X-射线衍射线(Cu Kα)。
此外，本发明包括一种制备铝磷酸盐或取代铝磷酸盐的方法，包括，形成SiO2、Al2O3和P2O5以及有机模版剂的反应混合物，所述反应混合物的组成以摩尔氧化物比率表示为1.5-3.0ROH∶Al2O3∶0.7-1.25P2O5∶0-0.4MOx∶40-80H2O，其中R是模版剂，且M＝Si、Ga、Ge、Co、Ni、Zn、Fe、Ti、V及其组合。所述模版优选为甲基三乙醇铵或二(2-羟乙基)二甲基铵。所述ECR-40具有特征X-射线衍射图，对于Cu Kα辐射的其基本线在表1中给出。线强度参考最强线，这时第一线在约11.35埃2θ处。随着特定的组成(P/Al/M比率)和特定模版及其在结构中的加入量(插入物)而发生较小变化。这时，强度使用最强线＝100，各强度括弧如下：
非常、非常强(vvs)＝100-70
非常强(vs) ＝70-50
强(s) ＝50-30
中等(m) ＝30-10
弱(w) ＝＜10
表1
优选实施方案的描述
| 晶面间距 | 线强度 |
| 11.35±0.20 | vvs. |
| 6.57±0.12 | m. |
| 5.08±0.10 | w. |
| 4.64±0.10 | mw. |
| 4.30±0.08 | m. |
| 4.15±0.08 | vs. |
| 4.02±0.08 | w. |
| 3.79±0.06 | s. |
| 3.35±0.06 | w. |
| 3.28±0.06 | m. |
| 3.09±0.06 | m. |
| 2.935±0.03 | mw. |
| 2.480±0.03 | mw. |
| 1.895±0.03 | w. |
如上所述，本发明是一种取代铝磷酸盐组合物及其制备方法。
实施例
实施例1
为了制备以下结构式的反应物组合物：
2ROH∶O.2 SiO2∶0.95 Al2O3∶0.95 P2O5∶50 H2O
其中R为模版，将12.9克Catapal A矾土与120.8克25％重量二(2-羟乙基)二甲基氢氧化铵水溶液(RSA Inc.)在搅拌器中混合10分钟，然后加入3克DuPont Ludox AS-40胶态硅石，随后是24.8克磷酸(85％)。持续搅拌10分钟。随后将52克等分试样度量到125毫升Parr Teflon衬底高压釜中并在162℃下反应。样品反应57天。将产物稀释，匀化并离心处理，倾析，洗涤并再次离心处理。固体产物是一种具有特性X-射线衍射花样的单相，其基本线在表1中给出且标引为具有尺寸a＝16.06埃，b＝11.34埃且c＝6.57埃的斜方晶单元晶胞，非常类似于铝硅酸盐组合物ZSM-18。在该制备工艺中，产物是具有棱柱(prizmatic)晶体的形式，其尺寸为0.1μm×1μm横截面和0.5μm×4μm长之间。该磷酸盐组合物标识为ECR-40。ICPAES化学分析得到如下组成：14.95％Al；12.97％P；4.36％Si，表示(Al0.49，Si0.14，P0.37)O2的ECR-40化学计量。
实施例2
使用50％重量二(2-羟乙基)二甲基氢氧化铵模版(RSA Inc.)溶液重新配制实施例1中的反应物配方，然后在160℃下反应24天。产物具有表1和图1所示的特征X-射线衍射图。在空气流中的热重量分析表明一种3阶段重量损失，包括与在约300℃和450℃下模版烧失有关的10％损失。在将该材料的样品在630℃下在空气中煅烧16小时并随后在88％RH下用水平衡之后，该样品增重23％。在21℃下对相同煅烧样品进行正己烷等温试验，得到16％重量的最大容量。对空气饱和的邻二甲苯的单点静态吸附得到17.5％重量的吸附容量，而对2，2-二甲基丁烷(DMB)的类似实验得到17.4％重量的容量，这证实了通道体系的大孔性质及其高孔容积。该产物的形态类似于实施例1的观察结果，其中纵横比大于约5。ICPAES化学分析得到15.99％Al；13.54％P；4.63％Si，表示(Al0.49，Si0.28，P0.33)O2的化学计量。
实施例3
该实施例说明，ECR-40可由预制的干燥SAPO凝胶合成。该SAPO凝胶可通过将以下组合物进行反应而制成：
O.2 SiO2∶0.95 Al2O3∶0.95P2O5即，将溶解在1200克水中的675克Al(NO3)3·9H2O与207克85％磷酸进行剧烈混合，然后加入溶解在250克水中的57克Na2SiO3·9H2O。慢慢加入氢氧化铵，直到在pH＝7.4时出现胶凝。将凝胶过滤并洗涤，在110℃下干燥60小时，随后粉碎成细粉末。该产物的化学分析表明组成比率为：O.13SiO2∶Al2O3∶P2O5。将10克该干燥凝胶与60克22.5％重量甲基三乙醇氢氧化物水溶液在125毫升Parr Teflon衬底的高压釜中，在170℃下反应43天，这时将该高压体系骤冷。分离和干燥之后的微晶产物具有表2和图1所示的特定的特征X-射线衍射图。表2的数据已暂时根据斜方晶单元晶胞来标引，大致具有轴线：a＝16.5埃；b＝11.4埃；c＝6.58埃。
表2
观测间距
建议标引
相对强度
2-θ d(A) h k l I/Io
| 7.782 | 11.3506 | 1 | 0 | 0 | 100.0 |
| 9.438 | 9.3630 | 1 | 0 | 1 | 0.3 |
| 11.018 | 8.0237 | 0 | 0 | 2 | 4.1 |
| 13.474 | 6.5663 | 0 | 1 | 0 | 13.0 |
| 15.578 | 5.6838 | 2 | 0 | 0 | 2.2 |
| 17.440 | 5.0809 | 0 | 1 | 2 | 6.9 |
| 18.315 | 4.8401 | 1 | 0 | 3 | 1.4 |
| 19.115 | 4.6392 | 2 | 0 | 2 | 9.7 |
| 20.656 | 4.2965 | 2 | 1 | 0 | 13.1 |
| 21.389 | 4.1508 | 0 | 1 | 3 | 55.6 |
| 22.102 | 4.0185 | 0 | 0 | 4 | 7.5 |
| 22.794 | 3.8980 | 2 | 0 | 3 | 1.4 |
| 23.464 | 3.7882 | 3 | 0 | 0 | 44.4 |
| 24.113 | 3.6878 | 3 | 0 | 1 | 1.7 |
| 25.974 | 3.4276 | 3 | 0 | 2 | 2.2 |
| 26.565 | 3.3526 | 2 | 1 | 3 | 7.5 |
| 27.163 | 3.2802 | 2 | 0 | 4 | 12.8 |
| 27.717 | 3.2159 | 3 | 1 | 1 | 3.0 |
| 28.831 | 3.0941 | 3 | 0 | 3 | 13.4 |
| 29.376 | 3.0379 | 3 | 1 | 2 | 3.3 |
| 30.438 | 2.9343 | 2 | 1 | 4 | 10.4 |
| 30.965 | 2.8855 | 0 | 1 | 5 | 2.4 |
| 31.425 | 2.8444 | 2 | 2 | 0 | 0.6 |
| 31.961 | 2.7979 | 1 | 1 | 5 | 5.0 |
| 32.459 | 2.7561 | 3 | 0 | 4 | 1.2 |
| 32.929 | 2.7178 | 1 | 2 | 3 | 2.7 |
| 33.425 | 2.6786 | 0 | 0 | 6 | 2.8 |
| 34.366 | 2.6074 | 1 | 0 | 6 | 1.3 |
| 34.830 | 2.5737 | 2 | 1 | 5 | 1.6 |
| 36.180 | 2.4807 | 4 | 1 | 2 | 9.7 |
| 37.919 | 2.3708 | 3 | 2 | 2 | 2.6 |
| 38.345 | 2.3455 | 4 | 1 | 3 | 2.3 |
| 39.611 | 2.2734 | 5 | 0 | 0 | 1.6 |
| 40.005 | 2.2519 | 3 | 2 | 3 | 3.2 |
| 41.225 | 2.1880 | 5 | 0 | 2 | 1.1 |
| 41.636 | 2.1674 | 0 | 1 | 7 | 1.0 |
| 42.024 | 2.1483 | 1 | 3 | 0 | 1.4 |
| 42.438 | 2.1282 | 4 | 0 | 5 | 0.6 |
| 42.798 | 2.1112 | 3 | 2 | 4 | 0.6 |
| 43.596 | 2.0744 | 5 | 1 | 2 | 0.9 |
| 44.328 | 2.0418 | 1 | 2 | 6 | 3.6 |
| 44.693 | 2.0260 | 4 | 1 | 5 | 2.0 |
| 45.787 | 1.9801 | 5 | 0 | 4 | 1.7 |
| 46.176 | 1.9643 | 3 | 2 | 5 | 0.9 |
| 47.990 | 1.8946 | 5 | 1 | 4 | 5.1 |
| 48.734 | 1.8670 | 4 | 1 | 6 | 2.1 |
| 49.008 | 1.8572 | 5 | 2 | 1 | 2.4 |
Claims (10)
1.一种大孔铝磷酸盐或取代铝磷酸盐，包括以下组成：
aR：(MxAlyPz)O2
其中R表示有机模版剂，且a＝0-0.4，X＝0-0.4，y＝0.35-0.5，且Z＝0.25-0.5，且特征在于表1的衍射图，且M可以是Si、Ga、Ge、Co、Ni、Zn、Fe、V、Ti及其组合。
2.根据权利要求1的组合物，其中R为甲基三乙醇铵。
3.根据权利要求1的组合物，其中R为三季铵阳离子。
4.根据权利要求1的组合物，其中R为二(2-羟乙基)二甲基铵阳离子。
5.一种制备根据权利要求1的组合物的方法，包括，将含有M的氧化物、Al2O3和P2O5、以及有机模版剂的源的反应混合物结晶，所述反应混合物的组成以摩尔氧化物比率表示为1.5-3.0ROH∶Al2O3∶0.7-1.25 P2O5∶0-0.4MOx∶40-80H2O，其中R是模版剂。
6.根据权利要求5的方法，其中M是硅。
7.根据权利要求5的方法，其中R为三季铵。
8.根据权利要求5的方法，其中R为二(2-羟乙基)二甲基氢氧化铵。
9.根据权利要求5的方法，其中R为甲基三乙醇铵。
10.根据权利要求5的方法，其中所述氧化物源衍生自预制的、预干燥的、无定形凝胶。
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/169,653 US5976491A (en) | 1998-10-09 | 1998-10-09 | Synthesis of and composition of ECR-40, large pore aluminophosphate |
| US09/169,653 | 1998-10-09 |
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| US (1) | US5976491A (zh) |
| EP (1) | EP1135330A4 (zh) |
| JP (1) | JP2002527328A (zh) |
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| CN100579904C (zh) * | 2007-03-07 | 2010-01-13 | 中国科学院大连化学物理研究所 | 一种中孔mnpa-8材料及其制备方法 |
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| KR970073723A (ko) * | 1996-05-17 | 1997-12-10 | 성기웅 | 새로운 구조를 갖는 결정성 알루미노포스페이트 분자체 조성물 및 그의 제조방법 |
| US7015174B2 (en) * | 2003-06-20 | 2006-03-21 | Exxonmobil Chemical Patents Inc. | Maintaining molecular sieve catalytic activity under water vapor conditions |
| EP2847132B1 (en) | 2012-05-08 | 2016-09-14 | ExxonMobil Chemical Patents Inc. | Synthesis of zeolite zsm-18 |
| CN103204484B (zh) * | 2013-04-09 | 2014-12-17 | 南开大学 | 一种有十元环和八元环交叉孔道的微孔亚磷酸铝及制备方法 |
| WO2014210560A1 (en) * | 2013-06-27 | 2014-12-31 | California Institute Of Technology | Molecular sieves with a linde type a topology and related methods and systems |
| KR102197599B1 (ko) * | 2018-10-11 | 2020-12-31 | 포항공과대학교 산학협력단 | 실리코알루미노포스페이트 분자체, 및 그 제조 방법, 이를 이용한 이산화탄소의 선택적 분리방법 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3699139A (en) * | 1969-10-16 | 1972-10-17 | Mobil Oil Corp | Synthetic crystalline aluminosilicate |
| US3950496A (en) * | 1973-05-29 | 1976-04-13 | Mobil Oil Corporation | Synthetic zeolite ZSM-18 |
| US4310440A (en) * | 1980-07-07 | 1982-01-12 | Union Carbide Corporation | Crystalline metallophosphate compositions |
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| US4793984A (en) * | 1984-04-13 | 1988-12-27 | Union Carbide Corporation | Molecular sieve compositions |
| US4778780A (en) * | 1987-07-23 | 1988-10-18 | Mobil Oil Corporation | Synthesis of crystalline SAPO-17 |
| GB8829924D0 (en) * | 1988-12-22 | 1989-02-15 | Ici Ltd | Zeolites |
| US4963337A (en) * | 1989-07-07 | 1990-10-16 | Chevron Research Company | Zeolite SSZ-33 |
| US5512267A (en) * | 1993-09-15 | 1996-04-30 | California Institute Of Technology | Zeolite CIT-1 |
| US5350570A (en) * | 1993-09-29 | 1994-09-27 | Mobil Oil Corp. | Synthesis of crystalline ZSM-18 |
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1998
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| CN100579904C (zh) * | 2007-03-07 | 2010-01-13 | 中国科学院大连化学物理研究所 | 一种中孔mnpa-8材料及其制备方法 |
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| KR20010079999A (ko) | 2001-08-22 |
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| CA2345254A1 (en) | 2000-04-20 |
| EP1135330A1 (en) | 2001-09-26 |
| AU1102700A (en) | 2000-05-01 |
| EP1135330A4 (en) | 2005-11-16 |
| KR100627545B1 (ko) | 2006-09-22 |
| JP2002527328A (ja) | 2002-08-27 |
| WO2000021884A1 (en) | 2000-04-20 |
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