CN113603108B - 一种O-Si-Al-Zr三元骨架AEI分子筛及其合成方法 - Google Patents
一种O-Si-Al-Zr三元骨架AEI分子筛及其合成方法 Download PDFInfo
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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 93
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 92
- 229910018580 Al—Zr Inorganic materials 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000005342 ion exchange Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- GEIAQOFPUVMAGM-UHFFFAOYSA-N Oxozirconium Chemical compound [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- WUPZNKGVDMHMBS-UHFFFAOYSA-N azane;dihydrate Chemical compound [NH4+].[NH4+].[OH-].[OH-] WUPZNKGVDMHMBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010949 copper Substances 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- GQABSXJCETZGRK-UHFFFAOYSA-N 6-azaniumylhexylazanium;dihydroxide Chemical compound [OH-].[OH-].[NH3+]CCCCCC[NH3+] GQABSXJCETZGRK-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical class C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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Abstract
本发明公开了一种O‑Si‑Al‑Zr三元骨架AEI分子筛及其合成方法。本发明以氢氧化六甲双铵为模板剂,锆溶胶为第三元骨架元素,经水热法合成D50=2~3微米左右的三元AEI分子筛。在AEI分子筛骨架中,采用锆来替代部分元素硅,其中锆以锆氧四面体替代了部分硅氧四面体进入分子筛的骨架,而不是像铜离子那样,只是通过离子交换与分子筛主体形成类似于盐的化合物。上述三元AEI分子筛经离子交换法加铜后,在尾气净化测试中,表现比二元AEI分子筛更好的热稳定性,对高温段去除氮氧化物有显著的改善。
Description
技术领域
本发明涉及一种AEI分子筛及其合成方法,属于无机催化材料技术领域。
背景技术
AEI分子筛是类似于SSZ-13分子筛结构的一个分支,是一类由八元环孔道构成的具有三维孔道结构的微孔分子筛,这种独特的孔道结构使得AEI分子筛近年来在催化剂气体吸附分离领域具有广泛的应用前景。近些年来,AEI分子筛主要用作制造汽车尾气净化器的催化剂,较SSZ-13分子筛具有更好的耐热性和催化效果。一般地,用于尾气净化的AEI分子筛是通过离子交换使布朗特酸和铜离子结合,形成的AEI铜。
尾气净化的原理就是使氮氧化物快速地还原成氮气,使燃烧不完全的有机残留物氧化成CO2。因为汽车尾气通过净化器时速度很快,上述的氧化还原反应必须在一瞬间完成,所以催化反应的速度是关键。改良催化性能的方式主要有以下两种,其一是改变掺入金属离子,其二是改变分子筛的骨架元素铝或硅,使部分铝或硅被其他元素所替代。就AEI分子筛催化剂而言,CN108786912A公开了一种含铜和铁双金属的AEI分子筛催化剂及其制备方法,通过离子交换的方式将Cu和/或Fe同时或分步负载到AEI分子筛上,制备得到含铜和铁双金属的AEI分子筛催化剂,该催化剂用于氮氧化物的选择性催化还原反应,表现出较宽的活性温度窗口以及水热稳定性。CN108786911A公开了一种含稀土的Cu-AEI分子筛催化剂及其制备方法,将含稀土元素的AEI分子筛与Cu的盐溶液进行离子交换,可得到含稀土元素的Cu-AEI分子筛催化剂。在合成过程中将稀土元素原位引入分子筛,不仅简化了制备过程,还可以提高分子筛的稳定性。上述专利文献均是通过离子交换方式与分子筛主体形成类似于盐的化合物,未见AEI分子筛的骨架材料中引入锆氧四面体的报道。
同时,目前在合成二元AEI分子筛时,几乎都是采用氢氧化N,N-二乙基-2,6-二甲基哌啶鎓作为模板剂,但是由于它的供应商极少,而且较贵,很难购买到合适的。
发明内容
本发明克服了上述现有技术的不足,提供了一种O-Si-Al-Zr三元骨架AEI分子筛及其合成方法。本发明以氢氧化六甲双铵(C12H32N2O2)为模板剂,锆溶胶为第三元骨架元素,经水热法合成D50=2~3微米左右的三元AEI分子筛。在AEI分子筛骨架中,采用锆来替代部分元素硅,其中锆以锆氧四面体替代了部分硅氧四面体进入分子筛的骨架,而不是像铜离子那样,只是通过离子交换与分子筛主体形成类似于盐的化合物。上述三元AEI分子筛经离子交换法加铜后,在尾气净化测试中,表现比二元AEI分子筛更好的热稳定性,对高温段去除氮氧化物有显著的改善。
本发明的技术方案是:一种O-Si-Al-Zr三元骨架AEI分子筛,其特征是,所述O-Si-Al-Zr三元骨架AEI分子筛中锆以锆氧四面体进入分子筛的骨架;以氢氧化六甲双铵为模板剂,锆溶胶为第三元骨架元素,经水热法制备而成。
上述O-Si-Al-Zr三元骨架AEI分子筛合成方法,其特征是,
其原料及其重量比为:
模板剂:氢氧化六甲双铵(C12H32N2O2);
硅源:铵型硅溶胶;
铝源:氢氧化铝;
锆源:锆溶胶;
碱源:氢氧化钠;
按重量比为:SiO2:Al2O3:ZrO2:Na2O:C12H32N2O2=100:(6~8.5):(0.2~3.5):(4~5.3):(31~43);
其合成方法具体包括以下步骤:
1)形成胶体状料浆
取氢氧化铝和氢氧化钠水溶液加热反应,生成偏铝酸钠,降至常温后加入模板剂氢氧化六甲双铵,搅拌10~20分钟,待用;
将锆溶胶和铵型硅溶胶混合,用高剪切力乳化器搅拌60~90分钟,待用;
2)水热反应
把上述两种混合液一起加到高压反应釜,密闭后开启搅拌,转速200~300rpm,加热升温至160℃时停止升温,保温反应36~72小时;
3)后处理
反应完毕后降至常温,经过滤、洗涤、焙烧(焙烧温度450~550℃),得三元AEI分子筛。
进一步的,焙烧完后的分子筛含有钠,用碳酸氢铵浸泡,得铵型分子筛,再次焙烧除氨,得氢型分子筛。
上述氢型分子筛可以进一步经离子交换掺入铜离子(氢型分子筛和醋酸铜一起做离子交换反应,铜离子进入分子筛),最终成为车用尾气净化器的催化剂材料。
进一步的,所述铵型硅溶胶的SiO2含量为30~40%(其余水和氨);所述氢氧化铝的Al2O3含量63~66%;所述氢氧化钠水溶液的Na2O含量为25~30%(其余水);所述锆溶胶的ZrO2含量为12~15%(其余水);模板剂中氢氧化六甲双铵含量~25%,其余为水。
优选的,各原料重量比按重量比为:SiO2:Al2O3:ZrO2:Na2O:C12H32N2O2=100:(7~8.5):(3~3.5):(4~5.3):(35~43)。
上述方法生产的O-Si-Al-Zr三元骨架AEI分子筛,粒度D50:2~3微米,比表面积:550~600m2/g,孔容:~0.3cc/g,其显微照片如图1所示。
本发明的有益效果是:
1、采用氢氧化六甲双铵作为模板剂,锆溶胶为第三元骨架元素,经水热法首次合成了D50=2~3微米左右的O-Si-Al-Zr三元AEI分子筛。虽然分子筛的化学组成含3~3.6%ZrO2,但XRD图并无偏移或杂相峰(见图3与图2的对比),可以认为是锆以锆氧四面体替代了部分硅氧四面体,是AEI分子筛的一种新型衍生物。
2、目前,氢氧化N,N-二乙基-2,6-二甲基哌啶鎓作为AEI分子筛合成中主要使用的模板剂,因其合成难度大,国内几乎找不到合适的供应商,并且其售价高,分子筛的成本难以降低;而采用氢氧化六甲双铵后,成本价格大幅度降低,适合工业化生产。
3、三元AEI分子筛经离子交换法加铜后,在尾气净化测试中,其表现比二元AEI更好的热稳定性,对高温段去除氮氧化物有显著的改善(二元AEI分子筛从500℃开始,催化性能会随温度升高而下降,三元AEI分子筛能很好地保持)。
附图说明
图1为O-Si-Al-Zr三元骨架AEI分子筛(氢型)的显微照片;
图2为二元骨架AEI分子筛(氢型)的XRD图;
图3为O-Si-Al-Zr三元骨架AEI分子筛(氢型)的XRD图;
图4为锆的加入量偏多(5%)的O-Si-Al-Zr三元骨架AEI分子筛(氢型)的XRD图。
具体实施方式
实施例所用原材料:铵型硅溶胶,SiO2=40%;氢氧化铝,Al2O3=65%;氢氧化钠溶液,Na2O=30%;锆溶胶:ZrO2=15%;模板剂中氢氧化六甲双铵含量=25%。
实施例1:(3.5%ZrO2)
1)形成料浆
取25.2克氢氧化铝和30.0克氢氧化钠水溶液加热反应,反应温度100℃,生成偏铝酸钠,降至常温后加入303克模板剂氢氧化六甲双铵,搅拌10分钟,待用;
把482.1克铵型硅溶胶和45.0克锆溶胶加到烧杯中,用高剪切力乳化器搅拌90分钟,待用;
2)把上述两种混合液一起加到高压反应釜,密闭后开启搅拌,转速280rpm,加热升温(升温速度0.8℃/分钟),至160℃时停止升温,保温72小时;
3)后处理
反应完毕后降至常温,经过滤、洗涤、烘干、焙烧(焙烧温度500℃),焙烧完后的分子筛含有钠,用65g/l的碳酸氢铵浸泡,得铵型分子筛,再次焙烧除氨(焙烧温度400℃),得三元AEI分子筛(氢型)。
上述方法制备的三元AEI分子筛(氢型),按重量比计,其中SiO2:85.81%、Al2O3:10.42%、ZrO2:3.77%,粒度D50:~3微米,比表面积:550~600m2/g,孔容:0.3cc/g,其显微照片如图1所示,XRD特征如图3所示。相比图2的二元AEI分子筛,其XRD图并无偏移或杂相峰,可以认为是锆以锆氧四面体替代了部分硅氧四面体,是AEI分子筛的一种新型衍生物。
对比实例:(5%ZrO2)
1)形成料浆
取25.2克氢氧化铝和30.0克氢氧化钠水溶液加热反应,反应温度100℃,生成偏铝酸钠,降至常温加入303克模板剂,搅拌10分钟,待用;
把482.1克硅溶胶和64.3克锆溶胶加到烧杯,用高剪切力乳化器搅拌90分钟,待用;
2)把上述两种混合液一起加到高压反应釜,密闭后开启搅拌,转速280rpm,加热升温(升温速度0.8℃/分钟),至160℃时停止升温,保温72小时;
3)后处理
反应完毕后降至常温,过滤、洗涤、烘干、焙烧(焙烧温度500℃),焙烧完后的分子筛含有钠,用65g/l的碳酸氢铵浸泡,得铵型分子筛,再次焙烧除氨(焙烧温度400℃),得三元AEI分子筛(氢型)。其XRD特征图如图4所示。
由图4可以看出:相比图3,分子筛中锆的加入量过多(此例~5%)时,在大约18°的地方出现了杂峰,其他地方也会出现小的变化,说明其中的锆没有全部进入晶格,一部分已经游离析出。因此,锆替代硅的数量是有限的。
实施例2:(3.07%ZrO2)
1)形成料浆
取25.2克氢氧化铝和30.0克氢氧化钠水溶液加热反应,反应温度100℃,生成偏铝酸钠,降至常温后加入303克模板剂氢氧化六甲双铵,搅拌10分钟,待用;
把482.1克铵型硅溶胶和39.5克锆溶胶加到烧杯中,用高剪切力乳化器搅拌80分钟,待用;
2)把上述两种混合液一起加到高压反应釜,密闭后开启搅拌,转速280rpm,加热升温(升温速度0.8℃/分钟),至160℃时停止升温,保温60小时;
3)后处理
反应完毕后降至常温,经过滤、洗涤、烘干、焙烧(焙烧温度500℃),焙烧完后的分子筛含有钠,用65g/l的碳酸氢铵浸泡,得铵型分子筛,再次焙烧除氨(焙烧温度400℃),得三元AEI分子筛(氢型),粒度D50:~2.4微米。
Claims (5)
1.一种O-Si-Al-Zr三元骨架AEI分子筛,其特征是,所述O-Si-Al-Zr三元骨架AEI分子筛中锆以锆氧四面体进入分子筛的骨架;以氢氧化六甲双铵为模板剂,锆溶胶为第三元骨架元素,经水热法制备而成;
其原料及其重量比为:
模板剂:氢氧化六甲双铵;
硅源:铵型硅溶胶;
铝源:氢氧化铝;
锆源:锆溶胶;
碱源:氢氧化钠;
按重量比为:SiO2:Al2O3:ZrO2:Na2O:C12H32N2O2=100:(7~8.5):(3~3.5):(4~5.3):(35~43);
其合成方法具体包括以下步骤:
1)形成胶体状料浆
取氢氧化铝和氢氧化钠水溶液加热反应,生成偏铝酸钠,降至常温后加入模板剂氢氧化六甲双铵,搅拌混匀,待用;
将锆溶胶和铵型硅溶胶混合,用高剪切力乳化器搅拌混匀,待用;
2)水热反应
把上述两种混合液一起加到高压反应釜,密闭后开启搅拌,加热升温至160℃时停止升温,保温反应36~72小时;
3)后处理
反应完毕后降至常温,经过滤、洗涤、焙烧,得三元AEI分子筛。
2.如权利要求1所述的一种O-Si-Al-Zr三元骨架AEI分子筛的合成方法,其特征是,所述步骤2)高压反应釜的搅拌转速为200~300rpm。
3.如权利要求1所述的一种O-Si-Al-Zr三元骨架AEI分子筛的合成方法,其特征是,所述铵型硅溶胶的SiO2含量为30~40%;所述氢氧化钠水溶液的Na2O含量为25~30%;所述锆溶胶的ZrO2含量为12~15%。
4.如权利要求1所述的一种O-Si-Al-Zr三元骨架AEI分子筛的合成方法,其特征是,所述焙烧完后的分子筛含有钠,用碳酸氢铵浸泡,得铵型分子筛,再次焙烧除氨,得氢型AEI分子筛。
5.一种车用尾气净化器的催化剂材料,其特征是,权利要求4所制备的氢型AEI分子筛进一步经离子交换掺入铜离子,制备成车用尾气净化器的催化剂材料。
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