CN106044792B - 一种晶体微孔亚磷酸铝nkx‑6同时作为磷源和铝源制备sapo‑34分子筛方法 - Google Patents
一种晶体微孔亚磷酸铝nkx‑6同时作为磷源和铝源制备sapo‑34分子筛方法 Download PDFInfo
- Publication number
- CN106044792B CN106044792B CN201610382991.3A CN201610382991A CN106044792B CN 106044792 B CN106044792 B CN 106044792B CN 201610382991 A CN201610382991 A CN 201610382991A CN 106044792 B CN106044792 B CN 106044792B
- Authority
- CN
- China
- Prior art keywords
- nkx
- silicon source
- crystalline microporous
- sapo
- aluminium phosphite
- 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.)
- Active
Links
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 39
- 239000010703 silicon Substances 0.000 title claims abstract description 38
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 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 23
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 22
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 13
- 239000011574 phosphorus Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 8
- 241000269350 Anura Species 0.000 title abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000009415 formwork Methods 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 8
- 229910001868 water Inorganic materials 0.000 claims abstract description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims abstract description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract 2
- 238000005406 washing Methods 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 6
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims 1
- 239000010457 zeolite Substances 0.000 abstract description 4
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
- 238000001816 cooling Methods 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
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000012805 post-processing Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 3
- 229910001593 boehmite Inorganic materials 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 150000002780 morpholines Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- AVPRDNCYNYWMNB-UHFFFAOYSA-N ethanamine;hydrate Chemical compound [OH-].CC[NH3+] AVPRDNCYNYWMNB-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001387 inorganic aluminate Inorganic materials 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 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 description 1
- 238000004809 thin layer chromatography Methods 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Landscapes
- 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
本发明提供了一种晶体微孔亚磷酸铝NKX‑6同时作为磷源和铝源制备SAPO‑34分子筛方法。晶体微孔亚磷酸铝NKX‑6(组成为Al7(HPO3)9(OH)6(C6H12N2H6)1.5(H2O)12)同时作为磷源和铝源,硅溶胶为硅源,有机模板剂为二乙胺,或吗啉,或四乙基氢氧化铵,或三乙胺等,将晶体微孔亚磷酸铝NKX‑6,硅源,有机模板剂,水按照Al2O3∶P2O3∶SiO2∶R∶H2O=1.0∶1.3∶(0.1~0.3)∶(2.0~3.0)∶(35~100)的摩尔组成混合,将该混合物在165‑200℃范围内和自生压力下水热晶化3~6天,然后冷却、水洗、分离、室温晾干,既得产品。采用本发明方法得到结晶度较高,骨架上硅分布更均匀的SAPO‑34分子筛产品。
Description
技术领域
本发明涉及硅磷酸铝分子筛SAPO-34的合成,具体讲是通过一种晶体微孔亚磷酸铝NKX-6,在硅溶胶与有机模板剂的作用下转化,制备骨架上硅含量低、硅分布更均匀的SAPO-34分子筛。
背景技术
硅磷酸铝分子筛SAPO-34由PO4,AlO4和SiO4四面体构成三维骨架结构,SAPO-34分子筛具有中等强度的酸性中心,同时具有八元环微孔结构,在甲醇制低碳烯烃反应中表现出优异的催化性能。
合成SAPO-34分子筛最常用的铝源和磷源分别是磷酸和拟薄水铝石或者异丙醇铝(催化学报,2016,37,227-233;Microporous and Mesoporous Materials 221(2016)128-136)。铝源和磷源间一经混合便会迅速反应。而合成SAPO-34分子筛最常用的硅源是硅溶胶,也可以使用其它硅源,如气相白炭黑、薄层层析、气相白炭黑等。上述硅源的组成均为二氧化硅,在形成反应混合物凝胶时,硅源处于高度聚集状态,由于反应体系中解聚二氧化硅能力较弱,导致在分子筛结构形成过程中硅源的解聚速度远低于磷酸铝的形成速度,因而不能以高度分散的形式进入骨架,大部以较高聚集态存在于SAPO-34的表面(Microporousand Mesoporous Materials 114(2008)416-423),导致合成的SAPO-34分子筛硅分布不均匀、难以控制,进而影响其催化反应性能。
发明内容
本发明是以晶体微孔亚磷酸铝NKX-6作为铝源和磷源,取代磷酸和拟薄水铝石或者异丙醇铝,通过晶体微孔亚磷酸铝与加入的硅源、有机模板剂反应,转化生成SAPO-34分子筛。文献(Chem.Mater.2007,19,4142-4147)报道了晶体微孔亚磷酸铝NKX-6的制备方法与结构,其组成为Al7(HPO3)9(OH)6(C6H12N2H6)1.5(H2O)12,骨架中铝的配位数为六配位,与拟薄水铝石中铝的配位数相似,更为重要的是在与加入的硅源、有机模板剂反应中,它的结构解聚转化速度与硅源的解聚速度匹配,从而保证了在SAPO-34分子筛成核、晶体的生长过程中,硅源以与磷源、铝源匹配状态进入SAPO-34分子筛骨架,因此,能很好地控制硅原子进入骨架的数量及形态,提高合成SAPO-34的催化反应性能。专利文献CN103253682A和ZL2013102407802分别报道了亚磷酸铝、微孔亚磷酸铝NKX-5为铝源合成Beta沸石的案例,但微孔亚磷酸铝在其中所起的作用与本申请存在明显差别,一是合成体系不同,微孔亚磷酸铝所起的作用也不同。上述专利文献研究的Beta沸石的组成是硅磷酸铝,需要在含有氢氧化钠的碱性体系中进行反应,亚磷酸铝、微孔亚磷酸铝NKX-5仅仅为其提供铝源,由于Beta沸石的硅铝比高,铝含量低,微孔亚磷酸铝在其制备过程中仅仅能发挥很小的作用。本申请所制备的SAPO-34硅磷酸铝分子筛的主要组成是磷酸铝,其中的磷源、铝源全部来自于同一化合物晶体微孔亚磷酸铝NKX-6,SAPO-34的形成完全受控于该晶体微孔亚磷酸铝NKX-6;二是晶体微孔亚磷酸铝NKX-6的结构与上述专利文献所提及的亚磷酸铝,NKX-5不同,在晶体微孔亚磷酸铝NKX-6的结构组成中含有一组八个Al-O-Al连接而成的环,是制备磷酸铝为主要组成的SAPO-34的良好铝源。
本发明经过下述步骤:将晶体微孔亚磷酸铝NKX-6、硅源、有机模板剂和水混合均匀,温度为15~35℃,然后将该混合物在165-200℃和自生压力下水热晶化3~6天,然后冷却、水洗、分离、室温晾干得到产物。
本发明以晶体微孔亚磷酸铝NKX-6(骨架组成Al7(HPO3)9(OH)6方法同Chem.Mater.2007,19,4142-4147)同时作为铝源和磷源,硅溶胶为硅源,有机模板剂为二乙胺,或吗啉,或四乙基氢氧化铵、或三乙胺,反应物料具有以下摩尔组成:Al2O3∶P2O3∶SiO2∶R∶H2O=1.0∶1.3∶(0.1~0.3)∶(2.0~3.0)∶(35~100)。
本发明的有益效果是:以晶体微孔亚磷酸铝NKX-6为磷源和铝源合成的SAPO-34分子筛,骨架硅分布更均匀,有助于改善其催化反应性能,为其在工业应用带来更好的前景。
下面结合附图与实施例对本发明进一步说明。
附图说明
图1是本发明实施例2所述的产品的粉末x射线衍射图(XRD)。
具体实施方案
实施例1
向6.3648g晶体微孔亚磷酸铝NKX-6中加入10mL去离子水,再依次加入0.26mL硅溶胶,3.33mL二乙胺,搅拌均匀后移入不锈钢反应釜中于200℃晶化6天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
实施例2
将6.3648g晶体微孔亚磷酸铝NKX-6在100℃下水热处理2h,取出后晾干,加入10mL去离子水,再依次加入0.53mL硅溶胶,3.33mL二乙胺,搅拌均匀后移入不锈钢反应釜中于165℃晶化3天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
实施例3
将6.3648g晶体微孔亚磷酸铝NKX-6在100℃下水热处理2h,取出后晾干,加入10mL去离子水,再依次加入0.53mL硅溶胶,4.47mL三乙胺,搅拌均匀后移入不锈钢反应釜中于200℃晶化5天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
实施例4
将6.3648g晶体微孔亚磷酸铝NKX-6在100℃下水热处理2h,取出后晾干,加入10mL去离子水,再依次加入0.79mL硅溶胶,4.47mL三乙胺,搅拌均匀后移入不锈钢反应釜中于180℃晶化5天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
实施例5
向2.2289g晶体微孔亚磷酸铝NKX-6中加入3mL去离子水,再依次加入0.28mL硅溶胶,6.86mL浓度为35%四乙基氢氧化铵,搅拌均匀后移入不锈钢反应釜中于170℃晶化4天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
实施例6
将6.3648g晶体微孔亚磷酸铝NKX-6在100℃下水热处理2h,取出后晾干,加入10mL去离子水,再依次加入0.79mL硅溶胶,1.48mL吗啉,搅拌均匀后移入不锈钢反应釜中于200℃晶化3天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
实施例7
将4.4579g晶体微孔亚磷酸铝NKX-6在100℃下水热处理2h,取出后晾干,加入10mL去离子水,再依次加入0.19mL硅溶胶,2.96mL吗啉,搅拌均匀后移入不锈钢反应釜中于200℃晶化4天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
实施例8
向2.2289g晶体微孔亚磷酸铝NKX-6中加入0.19mL硅溶胶,13.71mL浓度为35%四乙基氢氧化铵,搅拌均匀后移入不锈钢反应釜中于200℃晶化3天,然后按常规的分子筛后处理方法,冷却,洗涤,干燥,收集产品。
Claims (2)
1.一种晶体微孔亚磷酸铝NKX-6同时作为磷源和铝源制备SAPO-34分子筛方法,其特征在于经过下述步骤:将晶体微孔亚磷酸铝NKX-6、硅源、有机模板剂和水混合均匀,温度为15~35℃,然后将该混合物在165-200℃和自生压力下水热晶化3~6天,然后冷却、水洗、分离、室温晾干得到产物,反应物料具有以下摩尔组成:Al2O3∶P2O3∶SiO2∶R∶H2O=1.0∶1.3∶(0.1~0.3)∶(2.0~3.0)∶(35~100),其中硅源为硅溶胶,有机模板剂为二乙胺,或吗啉,或四乙基氢氧化铵,或三乙胺,Al2O3和P2O3是指所加入的晶体微孔亚磷酸铝NKX-6以Al2O3和P2O3计的比例。
2.按照权利要求1所述的一种晶体微孔亚磷酸铝NKX-6同时作为磷源和铝源制备SAPO-34分子筛方法,其特征在于反应混合物优选在200℃和自生压力下水热晶化5天,然后冷却、水洗、分离、室温晾干,既得产品。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610382991.3A CN106044792B (zh) | 2016-05-31 | 2016-05-31 | 一种晶体微孔亚磷酸铝nkx‑6同时作为磷源和铝源制备sapo‑34分子筛方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610382991.3A CN106044792B (zh) | 2016-05-31 | 2016-05-31 | 一种晶体微孔亚磷酸铝nkx‑6同时作为磷源和铝源制备sapo‑34分子筛方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106044792A CN106044792A (zh) | 2016-10-26 |
CN106044792B true CN106044792B (zh) | 2018-03-09 |
Family
ID=57172664
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610382991.3A Active CN106044792B (zh) | 2016-05-31 | 2016-05-31 | 一种晶体微孔亚磷酸铝nkx‑6同时作为磷源和铝源制备sapo‑34分子筛方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106044792B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109279623A (zh) * | 2018-10-12 | 2019-01-29 | 南开大学 | 一种用微孔亚磷酸铝nkx-12为铝源合成高硅铝比丝光沸石的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101531377A (zh) * | 2008-06-10 | 2009-09-16 | 上海第二工业大学 | 一种磷铝硅sapo-34高温水热合成方法 |
CN102795640A (zh) * | 2012-09-13 | 2012-11-28 | 南开大学 | 一种以哌嗪为模板剂合成sapo-34分子筛的方法 |
CN103172083A (zh) * | 2011-12-23 | 2013-06-26 | 正大能源材料(大连)有限公司 | 一种硅铝磷分子筛合成液体综合利用的方法 |
CN103253682A (zh) * | 2013-05-20 | 2013-08-21 | 南开大学 | 一种用结晶态亚磷酸铝为铝源合成β分子筛的方法 |
CN105271293A (zh) * | 2015-10-20 | 2016-01-27 | 复榆(张家港)新材料科技有限公司 | 一种高硅沸石的合成方法 |
-
2016
- 2016-05-31 CN CN201610382991.3A patent/CN106044792B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101531377A (zh) * | 2008-06-10 | 2009-09-16 | 上海第二工业大学 | 一种磷铝硅sapo-34高温水热合成方法 |
CN103172083A (zh) * | 2011-12-23 | 2013-06-26 | 正大能源材料(大连)有限公司 | 一种硅铝磷分子筛合成液体综合利用的方法 |
CN102795640A (zh) * | 2012-09-13 | 2012-11-28 | 南开大学 | 一种以哌嗪为模板剂合成sapo-34分子筛的方法 |
CN103253682A (zh) * | 2013-05-20 | 2013-08-21 | 南开大学 | 一种用结晶态亚磷酸铝为铝源合成β分子筛的方法 |
CN105271293A (zh) * | 2015-10-20 | 2016-01-27 | 复榆(张家港)新材料科技有限公司 | 一种高硅沸石的合成方法 |
Also Published As
Publication number | Publication date |
---|---|
CN106044792A (zh) | 2016-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108264057B (zh) | 一种固相合成浸润性可控的zsm-5沸石的方法 | |
CN108745410A (zh) | 一种含磷的多级孔zsm-5/y复合分子筛的制备方法 | |
CN101125665A (zh) | 液相晶化法制备sapo-34分子筛的方法 | |
CN104923293B (zh) | 邻甲酚异构化催化剂、其制备方法及利用其催化合成间对甲酚的方法 | |
CN102795640A (zh) | 一种以哌嗪为模板剂合成sapo-34分子筛的方法 | |
CN105174286B (zh) | 一种高比例aei/cha共晶分子筛的制备方法 | |
Wang et al. | Synthesis, characterization and crystallization mechanism of SAPOs from natural kaolinite | |
CN112794338B (zh) | Zsm-5分子筛及其制备方法和应用 | |
CN101555024A (zh) | 一种sapo-34分子筛的合成方法 | |
Lin et al. | Tetraalkylammonium salt/alcohol mixtures as deep eutectic solvents for syntheses of high-silica zeolites | |
CN108298550A (zh) | 一种以四氢呋喃与有机胺混合作为模板剂制备多级孔sapo-34分子筛的方法 | |
CN103058208B (zh) | Sapo-56分子筛的制备方法 | |
CN111099603A (zh) | Scm-18分子筛及其制备方法 | |
CN100395184C (zh) | 硅磷酸铝分子筛的合成方法 | |
CN106044792B (zh) | 一种晶体微孔亚磷酸铝nkx‑6同时作为磷源和铝源制备sapo‑34分子筛方法 | |
CN112209397A (zh) | 高锌硅比cha型拓扑结构锌硅分子筛及其合成方法 | |
CN103145145B (zh) | 一种以a型沸石为硅源合成sapo-34分子筛的方法 | |
CN102092737B (zh) | 一种AlPO4-34磷酸铝分子筛的合成方法 | |
Lu et al. | The structure-directing effect of n-propylamine in the crystallization of open-framework aluminophosphates | |
CN108314056B (zh) | 选择性合成sapo-15和sapo-34分子筛的方法 | |
CN101514004B (zh) | 共生分子筛及其合成方法 | |
CN106946267A (zh) | 一种eu-1分子筛及其合成方法 | |
CN106082266B (zh) | 两种微孔晶体配合转化制备sapo-34分子筛的方法 | |
CN102259890B (zh) | Zsm-5/ecr-1/丝光沸石三相共生材料及其制备方法 | |
CN106946270B (zh) | 一种Beta/EU-1复合分子筛及其合成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20180816 Address after: 116036 7 Ying Sheng Road, Ying Cheng zi Town, Ganjingzi District, Dalian, Liaoning Patentee after: Chia Tai Energy Materials (Dalian) Co., Ltd. Address before: 407 Patent and Intellectual Property Management Office, West Business Building, Jinnan Campus, 38 Tongyan Road, Haihe Education Park, Tianjin Patentee before: Nankai University |
|
TR01 | Transfer of patent right |