CN111099637A - 硅磷铝分子筛及其制备方法 - Google Patents
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- 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 133
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 131
- -1 Silicon-phosphorus-aluminum Chemical compound 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- 239000012452 mother liquor Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 22
- ATXBDDBELMGWOQ-UHFFFAOYSA-N [OH-].[NH4+].C1(=CC=C(C=C1)CC1N(CCC1)C)CC1N(CCC1)C Chemical compound [OH-].[NH4+].C1(=CC=C(C=C1)CC1N(CCC1)C)CC1N(CCC1)C ATXBDDBELMGWOQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000008025 crystallization Effects 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 2
- RHQQHZQUAMFINJ-GKWSUJDHSA-N 1-[(3s,5s,8s,9s,10s,11s,13s,14s,17s)-3,11-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-hydroxyethanone Chemical compound C1[C@@H](O)CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CC[C@H]21 RHQQHZQUAMFINJ-GKWSUJDHSA-N 0.000 claims 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 22
- 238000003786 synthesis reaction Methods 0.000 abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000003463 adsorbent Substances 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 238000003756 stirring Methods 0.000 description 36
- 238000001354 calcination Methods 0.000 description 12
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 5
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 241000269350 Anura Species 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 229910052908 analcime Inorganic materials 0.000 description 1
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910052676 chabazite Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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Abstract
本发明涉及一种新型的硅磷铝分子筛及其制备方法,所述分子筛在不计算水份的前提下具有如下摩尔比的化学组成:(SixAlyPz)O2,其中0<x≤0.2,y≥0.2,z≥0.2,且x+y+z=1,上述分子筛具有独特的X射线衍射图谱,它可以作为吸附剂使用,也可以作为催化剂应用于合成气制烯烃的反应中或者甲醇转化制烃类物质的反应中。
Description
技术领域
本发明涉及一种硅磷铝分子筛及其制备方法。
背景技术
分子筛是一类多孔的结晶材料,目前发现的已知结构的分子筛种类已达230多种,并且新结构的分子筛还在不断地涌现出来。大部分分子筛具有大的内比表面积以及开放的内部空间,这些内部空间既可以作为反应的发生场所,也可以用来容纳一些客体分子,如金属、金属氧化物,有机分子,水分子等等。由于分子筛具有均一规则的孔道,且孔道尺寸与分子属于同一量级,因而可以对分子的进出进行“选择”,从而获得择形效果。由于分子筛具有上述特征,因而被广泛用作催化剂、催化剂的载体、吸附剂和洗涤剂等,在石油化工,环保,以及吸附和分离领域获得了广泛应用。分子筛的骨架通常由配位四面体(TO4)通过共顶点(一般为氧原子)连接而成,对于沸石分子筛来说,骨架中的四面体主要为SiO4四面体和AlO4 -四面体,这两种四面体可以分别被其它的四面体所取代,从而形成许多各种骨架结构或者各种骨架组成的分子筛,例如,AlO4 -四面体可以被GaO4 -或ZnO4 2-四面体所取代,从而与SiO4四面体一道构成杂原子分子筛的骨架,而Ge与Si具有相似的配位性质,Ge也可以形成四面体配位结构,通过GeO4和SiO4的连接可以形成数量众多的新型含锗的分子筛结构。
如果SiO4四面体被PO4 +四面体所取代,则形成了分子筛家族的另一个大类,即磷酸铝分子筛,该类分子筛的骨架通过AlO4 -和PO4 +共氧原子连接而成,因而整个分子筛骨架呈现出电中性。当然,类似于沸石分子筛,磷酸铝分子筛中的铝氧四面体或者磷氧四面体也可以被其它的四面体所取代,其中最为常见的是硅氧四面体和锌氧四面体,由于这些四面体的引入,赋予了磷酸铝型分子筛新的特性。相比沸石分子筛,磷酸铝分子筛的人工合成研究比较晚。1971年,Flanigen等人报道了磷酸铝分子筛的合成【Molecular Sieve Zeolites-I,ACS,Washingtom D.C】,在水热合成条件下,混合铝,硅和磷的氧化物得到了与analcime,chabazite,phillipsite-harmotome,L型分子筛,A型分子筛和B型分子筛等具有相同晶体结构的硅磷铝分子筛,其中磷的含量为5~25%(以P2O5计),但没有发现区别于沸石分子筛的结构。1982年的美国专利4310440使用有机胺或者季铵类化合物作为模板剂,水热合成出了一系列的磷酸铝分子筛,它们包括:AlPO4-5,AlPO4-8,AlPO4-9,AlPO4-11,AlPO4-12,AlPO4-14,AlPO4-16,AlPO4-17,AlPO4-18,AlPO4-20,AlPO4-21,AlPO4-22,AlPO4-23,AlPO4-25,AlPO4-26,AlPO4-28,AlPO4-31等,对于磷铝分子筛的合成,有机模板剂的种类是决定其结构的关键因素之一,到目前为止,有机胺仍是磷铝分子筛合成中应用最为广泛的模板剂。相比硅铝沸石分子筛,磷铝分子筛的工业应用还不多见,目前只有SAPO-34分子筛和SAPO-11分子筛获得了工业上的应用。最近包信和等人【Science,2016,351,1065-1068】发表的文章揭示SAPO分子筛可以应用于合成气制烯烃反应中的耦合催化剂的一部分,获得了较好的催化效果,另外,磷酸铝分子筛的潜在应用还包括将它们作为吸附剂或者催化剂的良好载体。
发明内容
本发明所要解决的技术问题是提供一种现有技术中未涉及的新的硅磷铝分子筛及其合成方法。
为解决上述技术问题,本发明提供了一种硅磷铝分子筛,所述分子筛在不计算水分的前提下具有如下摩尔比的化学组成:(SixAlyPz)O2,其中0<x≤0.2,y≥0.2,z≥0.2,且x+y+z=1,更优选的范围是(SixAlyPz)O2,其中0<x≤0.1,y≥0.3,z≥0.3,且x+y+z=1。所述分子筛包含如下表所示的X射线衍射图谱:
其中,相对强度基于衍射峰的面积计算。
制备上述的硅磷铝分子筛,包括如下几个步骤:
a)将硅源,铝源,磷源,有机物R和水按照(0.01~0.3)SiO2:Al2O3:(1.0~3.0)P2O5:(3.0~6.0)R:(50~500)H2O的比例均匀混合,得到合成母液;
b)将上述合成母液置于密闭反应容器中进行晶化;
c)上述步骤b)获得的产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体;
d)将上述硅磷铝分子筛的前驱体焙烧,获得硅磷铝分子筛。
上述技术方案中,其中R为N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵,用化学结构式可以表示为:
上述技术方案中,将上述合成母液置于密闭反应容器中进行晶化,晶化温度为140℃~200℃,晶化时间为48~160小时,更优选的晶化条件是晶化温度为150℃~190℃,晶化时间为60~120小时。
上述技术方案中,将上述硅磷铝分子筛的前驱体按照常规的焙烧方法进行焙烧,比如在500~750℃,空气气氛下进行焙烧处理,即可获得硅磷铝分子筛。
上述技术方案中,硅源,铝源,磷源,有机物R和水按照(0.01~0.2)SiO2:Al2O3:(1.0~2.0)P2O5:(3.6~4.8)R:(100~300)H2O的比例均匀混合。
上述硅磷铝分子筛的制备方法,硅源为硅溶胶,白碳黑,或正硅酸四乙酯中的至少一种,铝源至少为拟薄水铝石,异丙醇铝,铝溶胶,氧化铝中的至少一种,磷源选自磷酸,亚磷酸或五氧化二磷中的一种或多种。
上硅磷铝分子筛的前驱体具有如下的X射线衍射图谱:
本发明得到的硅磷铝分子筛具有稳定的晶体结构,根据前驱体焙烧条件的不同,分子筛可能会有一定量的含碳物质的残留。
经过焙烧处理后得到的硅磷铝分子筛具有开放的孔道体系,它可以作为吸附剂使用,也可以作为催化剂应用于合成气制烯烃的反应中或者甲醇转化制烃类物质的反应中。
本发明提供了一种硅磷铝分子筛,在硅源,铝源,磷源,有机物R共同作用下,同时控制反应原料间的投料比,定向得到本发明所述硅磷铝分子筛。
附图说明
图1为实施例1所得Si-SCM-18分子筛前驱体的XRD图谱。
图2为实施例1所得Si-SCM-18分子筛的XRD图谱。
图3为实施例2所得Si-SCM-18分子筛前驱体的XRD图谱。
图4为实施例2所得Si-SCM-18分子筛的XRD图谱。
下面通过实施例对本发明作进一步的阐述,但并不因此限制本发明的保护范围。
具体实施方式
【实施例1】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,它具有如图1所示的XRD图谱。将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得硅磷铝分子筛(命名为Si-SCM-18,下同),其XRD图谱如图2所示,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.009Al0.5P0.491)O2。。
【实施例2】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为170℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,它具有如图3所示的XRD图谱。将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,其XRD图谱如图4所示,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.013Al0.5P0.487)O2。
【实施例3】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为150℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.009Al0.5P0.491)O2。
【实施例4】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为200℃,晶化时间为48小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.009Al0.5P0.491)O2。
【实施例5】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.017克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.02SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.007Al0.5P0.493)O2。
【实施例6】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.009克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.01SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.003Al0.5P0.497)O2。
【实施例7】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.043克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.05SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.013Al0.5P0.487)O2。
【实施例8】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.069克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.08SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.08Al0.5P0.42)O2。
【实施例9】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.087克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.1SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.022Al0.5P0.478)O2。
【实施例10】
称取20.7克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:3.6R:150H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为48小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.009Al0.5P0.491)O2。。
【实施例11】
称取20.7克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.069克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.08SiO2:1.0Al2O3:2.4P2O5:3.6R:150H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.018Al0.5P0.482)O2。。
【实施例12】
称取34.5克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:6.0R:260H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为48小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.009Al0.5P0.491)O2。。
【实施例13】
称取34.5克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.698克的拟薄水铝石和0.043克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.05SiO2:1.0Al2O3:2.4P2O5:6.0R:260H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为48小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.013Al0.5P0.487)O2。。
【实施例14】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.86克的异丙醇铝和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体。将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.01Al0.5P0.49)O2。。
【实施例15】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.86克的异丙醇铝和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为150℃,晶化时间为84小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体,将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.009Al0.5P0.491)O2。。
【实施例14】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.86克的异丙醇铝和0.026克的正硅酸四乙酯,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体。将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.01Al0.5P0.49)O2。。
【实施例15】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.86克的异丙醇铝和0.021毫升30%的Ludox LS-30溶液,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为190℃,晶化时间为60小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体。将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.01Al0.5P0.49)O2。。
【实施例16】
称取27.6克浓度为20.75%的N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵(以下简写为R)溶液,然后一边搅拌一边往其中加入0.86克的异丙醇铝和0.021毫升30%的Ludox LS-30溶液,随后再缓慢滴加2.30克浓度为85%的磷酸溶液,搅拌均匀后即可得到具有下述摩尔比例组成的合成母液:
0.03SiO2:1.0Al2O3:2.4P2O5:4.8R:190H2O
将上述合成母液置于密闭反应容器中进行晶化,晶化温度为150℃,晶化时间为120小时,晶化产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体。将上述硅磷铝分子筛的前驱体在550℃下焙烧5小时即可获得Si-SCM-18,所得Si-SCM-18分子筛的组成为(不计水含量)(Si0.01Al0.5P0.49)O2。。
Claims (10)
2.根据权利要求1所述的硅磷铝分子筛,其特征在于在不计算水分的前提下它具有如下摩尔比的化学组成:(SixAlyPz)O2,其中0<x≤0.1,y≥0.3,z≥0.3,且x+y+z=1。
3.根据权利要求1所述的硅磷铝分子筛的制备方法,包括如下几个步骤:
a)将硅源,铝源,磷源,有机物R和水按照(0.01~0.3)SiO2:Al2O3:(1.0~3.0)P2O5:(3.0~6.0)R:(50~500)H2O的比例均匀混合,得到合成母液;
b)将上述合成母液置于密闭反应容器中进行晶化;
c)上述步骤b)获得的产物经洗涤和干燥后,得到硅磷铝分子筛的前驱体;
d)将上述硅磷铝分子筛的前驱体焙烧即可获得硅磷铝分子筛。
4.根据权利要求3所述的硅磷铝分子筛的制备方法,其特征在于将硅源,铝源,磷源,有机物R和水按照(0.01~0.2)SiO2:Al2O3:(1.0~2.0)P2O5:(3.6~4.8)R:(100~300)H2O的比例均匀混合,得到合成母液。
5.根据权利要求3所述的硅磷铝分子筛的制备方法,其特征在于有机物R为N,N’-(1,4-亚苯基双(亚甲基))双(N-甲基吡咯烷)氢氧化铵。
6.根据权利要求3所述的硅磷铝分子筛的制备方法,其特征在于晶化温度为140℃~200℃,晶化时间为48~160小时。
7.根据权利要求3所述的硅磷铝分子筛的制备方法,其特征在于铝源至少为拟薄水铝石,异丙醇铝,铝溶胶,氢氧化铝或氧化铝中的一种。
8.根据权利要求3所述的硅磷铝分子筛的制备方法,其特征在于磷源选自磷酸,亚磷酸或五氧化二磷中的一种或多种。
9.根据权利要求3所述的硅磷铝分子筛的制备方法,其特征在于硅源为硅溶胶,白碳黑,或正硅酸四乙酯中的一种。
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