CN107840352B - Sapo分子筛膜的制备方法 - Google Patents
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- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- 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 60
- 241000269350 Anura Species 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003513 alkali Substances 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
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- 229910052593 corundum Inorganic materials 0.000 claims description 19
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- HHQMYHMTYIPFEG-UHFFFAOYSA-M [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P Chemical compound [O-2].[O-2].[O-2].[OH-].O.[Al+3].[Si+4].P HHQMYHMTYIPFEG-UHFFFAOYSA-M 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 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 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- 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 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 claims description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
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- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- -1 silicon-phosphorus-aluminum Chemical compound 0.000 description 12
- 239000007789 gas Substances 0.000 description 7
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/028—Molecular sieves
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- 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
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
本发明涉及一种硅磷铝SAPO分子筛膜的制备方法,主要改进现有SAPO分子筛膜制备技术不足的问题。本发明所述的方法包括对涂抹液中的硅源事先进行碱处理,先后在载体上涂覆晶种层和涂膜液,然后通过气相原位晶化制备分子筛膜。该技术方案操作简单,得到的SAPO分子筛膜重复性好,具有较好的致密性和均匀性,质量高,制备成本低,有利于模板剂的循环利用,可用于分子筛膜的工业生产中。
Description
技术领域
本发明涉及一种SAPO分子筛膜的制备方法。
背景技术
膜分离技术是一门新兴的分离、提纯和净化技术,目前已广泛用于食品、饮料、冶金、造纸、纺织、制药、汽车、生物和化工等领域。按膜材料不同,可以分为无机膜和有机膜,与有机膜相比,无机膜具有优异的化学稳定性、热稳定性和机械强度。分子筛膜,作为无机膜中具有代表性的一种,它的孔道具有一定的形状且结构可控、孔径可调且分布均匀、孔径大小与分子尺寸相近。由于分子筛膜特异的孔结构,因此具有选择透过性和择形催化作用,并且还可以通过离子交换对分子筛膜进行改性。分子筛膜在分子水平的分离和催化作用使其在膜分离、膜催化和膜反应器等领域有诱人的应用前景,近年来已成为无机膜材料的研究热点。
分子筛膜可分为填充膜(嵌入膜)、自支撑膜和支撑膜这三大类,由于支撑分子筛膜具有分子筛所有的特点而成为最具有开发潜力的一类分子筛膜。支撑分子筛膜的制备方法主要四类,分别是水热原位生成法、二次生长法、微波合成法及气相晶化法。其中二次生长法是最常用的一种制膜方法,即先在支撑体上附着上一层预合成的纳米级分子筛晶体作为晶种,再浸入合成液中继续晶化,从而促进分子筛晶种内平面的生长减少裂缝,形成连续分子筛膜。气相晶化法制备分子筛膜主要是将合成液通过旋涂法或浸渍法涂覆在支撑体或预附着晶种的支撑体上,再通过气相转移法晶化得到分子筛膜,此法避免了水热晶化造成的膜层较厚以及模板剂大量使用造成的资源浪费。
上述分子筛膜的制备方法中,其硅源均为直接使用,晶粒不均匀,颗粒较大,形成的分子筛膜缺陷多,不利于用于混合气的分离;原位生成法和二次生长法是通过水热体系使分子筛成核和生长,因此对粒子形状和载体上晶核的密度无法控制,从而使得载体上的膜不均匀,此外,由于合成液用量大,使得制备成本高,废液量大;原位生成法不使用晶种,导致分子筛膜致密性低;分子筛膜的研究主要集中在硅铝氧化物材料上,对于硅磷铝分子筛膜的研究较少,从膜制备技术、制备成本、分离效果等方面离工业应用要求还有很大差距,有待进一步研究解决。
为了克服上述缺陷,特别需要一种高质量、简易并且环保的合成硅磷铝分子筛膜的制备方法。
发明内容
本发明所要解决的技术问题是改进现有SAPO分子筛膜制备技术不足的问题。本发明提供了一种新的SAPO分子筛膜的制备方法,该材料具有较好的致密性和重复性。
为解决上述技术问题之一,本发明采用的技术方案如下:一种SAPO分子筛膜的制备方法,包括以下步骤:
a)将载体分别用0.1%~2%的酸和0.1%-2%的碱浸泡0.5~48小时后,清洗至中性,干燥,焙烧后待用;
b)将晶种涂覆在处理后的载体上;
c)将磷源、铝源、碱处理后的硅源和水在-20℃~100℃条件下混合均匀,得到硅磷铝氧化物溶胶,其中,磷源按理论生成P2O5量计、铝源按理论生成Al2O3量计、硅源按理论生成SiO2量计,混合物重量比组成为:H2O/Al2O3=1~200;SiO2/Al2O3=0.03~0.90;P2O5/Al2O3=0.05~2.80;所述碱处理具体实现为将硅源放置在碱性溶液中加热回流;
d)将上述硅磷铝氧化物溶液涂覆在经过b)步骤的载体上,干燥后置于反应釜上部,反应釜底部加入有机胺与水的混合物,有机胺/水=0.001~2,在150-220℃下反应0.1-5天;
(e)反应结束后反应釜冷却,然后用去离子水对样品进行冲洗,干燥得到SAPO型分子筛膜。
上述步骤中,将磷源、铝源、碱处理后的硅源和水在-20℃~100℃条件下混合均匀,较好的,将铝源混合于水中,边搅拌的同时加入磷源,强烈搅拌3-4h使其完全水解且得到白色奶状的均匀溶液,然后加入碱处理后的硅源,搅拌得到硅磷铝氧化物溶胶。以提高分子筛膜的致密性。上述技术方案中,处理载体的碱选自氢氧化钠、氢氧化钾、氨水、四乙基氢氧化胺、四乙基溴化铵、三乙胺或乙二胺中的至少一种;酸选自盐酸、硝酸或硫酸中的至少一种。
所述酸碱浸泡的浓度为0.2%~1.5%,处理时间为1~24小时。
所述晶种的涂覆方式采用涂膜或提拉中的至少一种,较好的,提拉数次。
所述硅源选自硅溶胶,正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯、正硅酸四丁酯或硅溶胶中的至少一种;铝源选自异丙醇铝、拟薄水铝石、氧化铝、硝酸铝、氯化铝或硫酸铝中的至少一种;磷源选自磷酸、磷酸铵、磷酸氢二铵、磷酸氢铵、磷酸钾、磷酸氢二钾、磷酸氢钾、磷酸钠、磷酸氢二钠或磷酸氢钠中的至少一种。
所述硅磷铝混合物重量比组成选自:H2O/Al2O3=3.00~13.00;SiO2/Al2O3=0.07~0.80;P2O5/Al2O3=0.06~2.30;;有机胺/水=0.003~1之间。
所述有机胺模板剂选自四乙基氢氧化胺、三乙胺或乙二胺中的至少一种。
所述晶化温度为40~210℃,晶化时间为0.2~4天。
所述载体为氧化铝。
本发明通过对硅源进行碱处理,将硅源分解为均匀的二氧化硅小粒子,使得生成的硅磷铝分子筛膜致密性好,缺陷少。将二次生长法和气相晶化法有机结合,得到的硅磷铝分子筛膜连续性好,硅磷铝分子筛膜的厚度容易控制,且较致密,重复性好。通过气相晶化得到硅磷铝分子筛膜,并且通过调节晶化次数可以进一步调控硅磷铝分子筛膜的厚度。本发明制备过程简单,容易控制,结晶度高,硅磷铝分子筛膜质量高,取得了较好的技术效果。
附图说明
图1为【实施例1】得到的SAPO分子筛膜的扫描电镜(SEM)照片。
图2为【实施例1】得到的SAPO分子筛膜的X光线衍射(XRD)图谱。
下面通过实施例对本发明作进一步的阐述。
具体实施方式
【实施例1】
将12.3g的异丙醇铝混合于离子水中,边搅拌的同时加入11.97g磷酸,强烈搅拌3-4h使其完全水解且得到白色奶状的均匀溶液。然后加入6g在碱液中回流处理后的硅溶胶,在室温下搅拌3h。将经过预处理且预涂晶种的载体管两端密封后,垂直放入上述混合液中,提拉数次,室温凉干后置于带有聚四氟乙烯衬体的不锈钢反应釜上部,反应釜底部加入3g模板剂四乙基氢氧化铵和10g水的混合溶液,密封后在和自身压力下静止晶化48h。晶化完毕取出载体,然后用去离子水反复洗涤数次直至溶液的值为中性,然后干燥、焙烧后得到SAPO分子筛膜。XRD结果表明,所得产品为SAPO分子筛膜。SEM见图1,XRD结果见图2。
各组分的重量比为:SiO2/Al2O3=0.4;P2O5/Al2O3=1.1;H2O/Al2O3=7
【实施例2~14】
按照【实施例1】的各个步骤及条件,制得SAPO分子筛膜,只是改变原料(表1)配比、模板剂种类、晶化温度等参数,具体列于表1。合成的产物经表征说明其结果具有与【实施例1】、产物相似的晶体结构。
表1
【实施例15】传统方法制备分子筛膜
称取12.3g异丙醇铝、11.97g的磷酸、6g硅溶胶,和60g模板剂R1混合,搅拌3h,形成混合液A。将经过涂覆晶种的载体管两端密封后,垂直放入带有聚四氟乙烯衬体的不锈钢反应釜中,然后将混合液A倒入,密封后在自身压力下静止晶化24h。晶化完毕取出载体,然后用去离子水反复洗涤数次直至溶液的值为中性,然后干燥、焙烧后得到传统方法制备的SAPO-34分子筛膜。各组分的重量比为:SiO2/Al2O3=0.4;P2O5/Al2O3=1.1;H2O/Al2O3=7;R1/Al2O3=10
对实施例1制备的分子筛膜(A)和传统方法制备的分子筛膜(B)进行CO2和CH4混合气进行分离,结果如下所示。
Claims (8)
1.一种SAPO分子筛膜的制备方法,包括以下步骤:
a)将载体分别用0.1%~2%的酸和0.1%-2%的碱浸泡0.5~48小时后,清洗至中性,干燥,焙烧后待用;
b)将晶种涂覆在处理后的载体上;
c)将磷源、铝源、碱处理后的硅源和水在-20℃~100℃条件下混合均匀,得到硅磷铝氧化物溶胶,其中,磷源按理论生成P2O5量计、铝源按理论生成Al2O3量计、硅源按理论生成SiO2量计,混合物重量比组成为:H2O/Al2O3=1~200;SiO2/Al2O3=0.03~0.90;P2O5/Al2O3=0.05~2.80;所述碱处理具体实现为将硅源放置在碱性溶液中加热回流;
d)将上述硅磷铝氧化物溶液涂覆在经过b)步骤的载体上,干燥后置于反应釜上部,反应釜底部加入有机胺与水的混合物,其中有机胺/水=0.001~2,在150-220℃下反应0.1-5天;
(e)反应结束后反应釜冷却,然后用去离子水对样品进行冲洗,干燥得到SAPO型分子筛膜。
2.根据权利要求1所述SAPO分子筛膜的制备方法,其特征在于步骤a)中处理载体的碱选自氢氧化钠、氢氧化钾、氨水、四乙基氢氧化胺、四乙基溴化铵、三乙胺或乙二胺中的至少一种;酸选自盐酸、硝酸或硫酸中的至少一种。
3.根据权利要求1所述SAPO分子筛膜的制备方法,其特征在于步骤a)中酸碱浸泡的浓度为0.2%~1.5%,处理时间为1~24小时。
4.根据权利要求1所述SAPO分子筛膜的制备方法,其特征在于步骤b)中晶种的涂覆方式采用涂膜或提拉中的至少一种。
5.根据权利要求1所述SAPO分子筛膜的制备方法,其特征在于步骤c)中其中硅源选自正硅酸四甲酯、正硅酸四乙酯、正硅酸四丙酯、正硅酸四丁酯或硅溶胶中的至少一种;铝源选自异丙醇铝、拟薄水铝石、氧化铝、硝酸铝、氯化铝或硫酸铝中的至少一种;磷源选自磷酸、磷酸铵、磷酸氢二铵、磷酸氢铵、磷酸钾、磷酸氢二钾、磷酸氢钾、磷酸钠、磷酸氢二钠或磷酸氢钠中的至少一种。
6.根据权利要求1所述SAPO分子筛膜的制备方法,其特征在于步骤c)中混合物重量比为:H2O/Al2O3=3.00~13.00;SiO2/Al2O3=0.07~0.80;P2O5/Al2O3=0.06~2.30;有机胺/水=0.003~1。
7.根据权利要求1所述SAPO分子筛膜的制备方法,其特征在于步骤c)中有机胺模板剂选自四乙基氢氧化胺、四乙基溴化铵、三乙胺或乙二胺中的至少一种。
8.根据权利要求1所述SAPO分子筛膜的制备方法,其特征在于步骤c)中晶化温度为40~210℃,晶化时间为0.2~4天。
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