CN107285343A - 一种分子筛的合成方法 - Google Patents
一种分子筛的合成方法 Download PDFInfo
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- CN107285343A CN107285343A CN201710436097.4A CN201710436097A CN107285343A CN 107285343 A CN107285343 A CN 107285343A CN 201710436097 A CN201710436097 A CN 201710436097A CN 107285343 A CN107285343 A CN 107285343A
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 11
- 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 11
- 238000010189 synthetic method Methods 0.000 title claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical group CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000002360 explosive Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
- 150000001336 alkenes Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 238000009415 formwork Methods 0.000 abstract 1
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
一种分子筛的合成方法,该方法包括将硅、磷、铝源,水混合成胶,将该混合物加热到180‑250℃,水热法反应12‑48小时,本发明的特征在于使用磷酸乙胺为磷源,采用无易燃易爆的有机模板剂,和强腐蚀性磷酸的工艺条件制备沸石,使制备过程简使易行,更适合于工业化生产。该分子筛可以用于甲醇制烯烃反应,以及汽车等尾气中氮化物的去除。
Description
技术领域
本发明涉及一种分子筛的合成方法。
背景技术
分子筛由P02+,A102-和Si02三种四面体相互连接而成,具有椭球形笼、圆形或起皱形结构。具有中等酸性以及良好的热稳定性和水热稳定性,它对甲醇催化制制取烯烃反应表现出优异的催化性能而受关注。此分子筛的合成早些年有美国专利报道使用四乙基氢氧化铵为模板剂，后来中国专利中也有公开使用二乙胺为模板剂来准备，但是这些模板剂都较为昂贵。后来中国专利中也有报道采用一些廉价的模板剂来取代，成本又所下降，但无论哪种方法，它们都是用有机胺为模板剂，而有机胺为易燃易爆品,给工业化过程带来麻烦。
发明内容
本发明目的在于提供一种分子筛,具有制备工艺更安全,更适合工业化生产。其特征在于:釆用无模板剂工艺条件。硅源可以是硅溶胶H氣化硅,铝源可为烷氧基铝、氢氧化铝或活性氧化铝，磷源可以是磷酸胺等。其制备工艺为:
将水,磷源,铝源,硅源混合成胶,在35-100℃下,搅拌180分钟,加入一定量的晶种,然后将上述混合物加热到180-250℃和自生圧力下进行水热反应12-48小时。
晶化完全后过、滤或离心分高,必要时,可以进行高子交换,水洗,以去除杂质；然后进行干燥,焙烧。
下面用实例进一步详细说明本发明,但是本发明不受这些实施例的限制。
具体实施方式
实施例1
将173.1克的磷酸乙胺,145.7克的拟薄水铝石(以氧化物计的主含量为70％)，120克溶胶(以氧化硅的主含量为30％),加入900克去离子水中,投入高压反应釜中,在室温条件下,开启搅拌,转速为300转/分钟,搅拌5小试,成胶。加入晶种15克,搅拌30分钟后,升温到200℃,在自生压力下反应36小时。
过滤分离出目标产物，并将此滤饼加入5％的硝酸铵溶液中进行离子交换，取出其中的杂质，过滤、洗涤。将滤饼放入烘箱中，4小时干燥，取部分样品进行X-射线粉末衍射分析，所得样品为SAPO-34。
Claims (4)
1.一种分子筛的合成方法,其特征在于:首先将铝源,硅源,磷源和水,混合成胶,成胶温度范围为:35-100℃。铝源,硅源,磷源成胶时,以氧化物的摩尔比为:0.02-1.5:0.02-1.5:0.02-1；其中水与氧化铝的摩尔比为15-50。其特征在于磷源是磷酸乙胺。在搅拌状态下维持180分钟。可以加入一定量的晶种,然后将上述混合物加热到180-250℃,在自身压力下进行水热反应12-48小时。晶化完全后过滤,再进行离子交换,过滤,洗涤，干操,焙烧。
2.根据权利要求1所述的分子筛的合成方法,干燥可在50-180℃的条件下进行；焙烧可以在250-800℃范围内进行；高子交换剂可以选择固体硝酸铵。
3.根据权利要求2,离子交换剂可以是硝酸铵溶液,或硝酸与氨水的反应混合物。
4.权利要求1所述分子筛的合成方法,其特征在于是硅源可以是硅溶胶、活性二氧化硅,铝源可为氢氧化铝或活性氧化铝；磷源是磷酸胺。
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134081A (zh) * | 2010-01-25 | 2011-07-27 | 天津海赛纳米材料有限公司 | 无模板剂存在下一种sapo-34分子筛的合成方法 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102134081A (zh) * | 2010-01-25 | 2011-07-27 | 天津海赛纳米材料有限公司 | 无模板剂存在下一种sapo-34分子筛的合成方法 |
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Application publication date: 20171024 |