CN110560146A - 一种双金属mel分子筛及其制备方法和应用 - Google Patents
一种双金属mel分子筛及其制备方法和应用 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 94
- 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 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 51
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 32
- 239000010949 copper Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 229910052710 silicon Inorganic materials 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 13
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000013110 organic ligand Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005269 aluminizing Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910021485 fumed silica Inorganic materials 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000002149 hierarchical pore Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000003760 magnetic stirring Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 150000007530 organic bases Chemical class 0.000 description 7
- 229960002413 ferric citrate Drugs 0.000 description 6
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 5
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005216 hydrothermal crystallization Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- WUOUGWUVWNZBIU-UHFFFAOYSA-N 2-benzyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1CC1=CC=CC=C1 WUOUGWUVWNZBIU-UHFFFAOYSA-N 0.000 description 1
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 229940054021 anxiolytics diphenylmethane derivative Drugs 0.000 description 1
- MKHQMLKDCBPKBC-UHFFFAOYSA-N benzene;copper(1+) Chemical compound [Cu+].C1=CC=[C-]C=C1 MKHQMLKDCBPKBC-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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- B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
- B01J29/0356—Iron group metals or copper
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Abstract
本发明属于分子筛材料技术领域，尤其涉及一种双金属MEL分子筛及其制备方法和应用。本发明提供了一种双金属MEL分子筛，所述双金属MEL分子筛具有介孔和微孔，所述介孔和所述微孔内负载有Cu和Fe；所述双金属MEL分子筛的硅铝比为48～50。本发明双金属MEL分子筛为H‑MEL@Cu/Fe双金属分子筛催化剂，该双金属MEL分子筛具有介孔和微孔，具有多级孔结构，而且Cu和Fe金属在分子筛骨架中不容易浸出，本发明双金属MEL分子筛可作为催化剂，在三甲苯和苯甲醇的傅‑克烷基化反应中能表现出优异的催化性能，Cu和Fe双金属的协同作用不仅能够提高烷基化的活性还提高了选择性，拓宽了分子筛催化剂在化工领域应用的前景。
Description
技术领域
本发明属于分子筛材料技术领域，尤其涉及一种双金属MEL分子筛及其制备方法和应用。
背景技术
傅-克烷基化反应在石油化工生产过程中能够合成高价值的二苯甲烷及二苯甲烷衍生物，在工业应用中通常是使用均相催化剂，这些均相催化剂的固有缺点是它们具有毒性，难以分离和再生。而分子筛具有良好的水热稳定性、高比表面积、酸度可调、回收再生容易和对人体没有毒害等优点，因此在傅-克烷基化反应中具有广阔应用的前景。
但是，催化过程中活性和选择性一直是催化剂设计和应用的难题。因此，寻求一种活性和选择性俱佳的分子筛催化剂一直是本领域技术人员亟待解决的问题。
发明内容
有鉴于此，本发明提供了一种双金属MEL分子筛及其制备方法和应用，该双金属MEL分子筛作为傅-克烷基化反应催化剂，活性和选择性俱佳。
一种双金属MEL分子筛，所述双金属MEL分子筛具有介孔和微孔，所述介孔和所述微孔内负载有Cu和Fe；
所述双金属MEL分子筛的硅铝比(Si/Al)为48～50。
本发明双金属MEL分子筛为H-MEL@Cu/Fe双金属分子筛催化剂，该双金属MEL分子筛具有介孔和微孔，具有多级孔结构，而且Cu和Fe金属在分子筛骨架中不容易浸出，能够克服金属容易发生团聚和浸出的问题，本发明双金属MEL分子筛可作为催化剂，Cu和Fe双金属的协同作用不仅能够提高傅-克烷基化的活性还提高了选择性，使得本发明双金属MEL分子筛在三甲苯和苯甲醇的傅-克烷基化反应中能表现出优异的催化性能，活性和选择性俱佳。
优选的，所述介孔的孔径为2nm～3.8nm，所述微孔的孔径为0.59nm以下。
本发明还提供了上述技术方案所述双金属MEL分子筛的制备方法，包括以下步骤：
a)将硅源、模板剂、铁源、铜源和去离子水混合，得到第一产物；
b)将所述第一产物进行晶化，得到第二产物；
c)将所述第二产物在含有铝源的有机碱处理液中水热条件下进行脱硅加铝，再依次进行干燥和焙烧，得到双金属MEL分子筛。
优选的，步骤a)所述硅源选自正硅酸乙酯、气相二氧化硅和硅胶中的一种或多种，更优选为正硅酸乙酯；
所述模板剂选自四丁基氢氧化铵、四乙基氢氧化铵和四丙基氢氧化铵中的一种或多种，更优选为四丁基氢氧化铵；
所述铁源为有机配体铁，所述铜源为有机配体铜。
有机配体铁选自柠檬酸铁、乙酰丙酮铁和二茂铁中的一种或多种，优选为柠檬酸铁；
有机配体铜选自乙酰丙酮铜、苯基铜和柠檬酸铜中的一种或多种，优选为乙酰丙酮铜。
铝源选自异丙醇铝、偏铝酸钠和铝酸钠中的一种或多种，优选为异丙醇铝；
有机碱选自四丁基氢氧化铵、四乙基氢氧化铵和四丙基氢氧化铵中的一种或多种，优选为四丁基氢氧化铵。
优选的，所述硅源、所述模板剂、所述铁源、所述铜源和所述去离子水的摩尔比为1:0.25：(0.005～0.015)：0.02：(20～30)，优选为1:0.25：0.01：0.02：25。
本发明中，步骤a)优选为在室温磁力搅拌下，将硅源、模板剂和去离子水进行混合均匀制备成混合液，再将铁源和铜源在磁力搅拌下加入至混合液中并混合均匀，得到第一产物。
优选的，步骤b)所述晶化的温度为165℃～170℃；
所述晶化的时间为72h～96h。
本发明中，晶化之后，优选进行过滤、洗涤和干燥，干燥的温度优选为100℃～105℃，干燥的时间优选为12h，得到的第二产物为全硅P-MEL@Cu/Fe分子筛。
优选的，步骤c)所述脱硅加铝的温度为165℃～170℃，所述脱硅加铝的时间为72h～96h；
干燥的温度为100℃～105℃，干燥的时间为12h；
所述焙烧的温度为500℃～550℃，所述焙烧的时间为5h～6h，更优选为6h。
步骤c)进行脱硅加铝之后，优选进行过滤、洗涤，再依次进行干燥和焙烧，得到的双金属MEL分子筛为H-MEL@Cu/Fe分子筛。
本发明还提供了上述技术方案所述双金属MEL分子筛和/或上述技术方案所述制备方法制得的双金属MEL分子筛作为催化剂的应用。
优选的，所述催化剂为傅-克烷基化反应催化剂。
优选的，所述傅-克烷基化反应的反应底物为三甲苯和苯甲醇。
本发明双金属MEL分子筛作为傅-克烷基化反应催化剂，Cu和Fe双金属的协同作用不仅能够提高傅-克烷基化的活性还提高了选择性，使得本发明双金属MEL分子筛在三甲苯和苯甲醇的傅-克烷基化反应中能表现出优异的催化性能，活性和选择性俱佳。
综上所述，本发明提供了一种双金属MEL分子筛，所述双金属MEL分子筛具有介孔和微孔，所述介孔和所述微孔内负载有Cu和Fe；所述双金属MEL分子筛的硅铝比为48～50。本发明双金属MEL分子筛为H-MEL@Cu/Fe双金属分子筛催化剂，该双金属MEL分子筛具有介孔和微孔，具有多级孔结构，而且Cu和Fe金属在分子筛骨架中不容易浸出，本发明双金属MEL分子筛可作为催化剂，在三甲苯和苯甲醇的傅-克烷基化反应中能表现出优异的催化性能，Cu和Fe双金属的协同作用不仅能够提高烷基化的活性还提高了选择性，拓宽了分子筛催化剂在化工领域应用的前景。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍。
图1为本发明实施例1制备得到的双金属MEL分子筛的X射线衍射图。
图2为本发明实施例1制备得到的双金属MEL分子筛的扫描电镜图。
图3为本发明实施例1制备得到的双金属MEL分子筛的透射电镜图。
图4为本发明实施例1制备得到的双金属MEL分子筛Fe的XPS图(704～738eV)；
图5为本发明实施例1制备得到的双金属MEL分子筛Cu的XPS图(926～964eV)；
图6为本发明实施例1制备得到的双金属MEL分子筛的氮气吸附脱附等温线；
图7为本发明实施例1制备得到的双金属MEL分子筛的NLDFT孔径分布图；
图8为本发明实施例1制备得到的双金属MEL分子筛的BJH孔径分布图。
具体实施方式
本发明提供了一种双金属MEL分子筛及其制备方法和应用，该双金属MEL分子筛作为傅-克烷基化反应催化剂，活性和选择性俱佳。
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
本实施例进行双金属MEL分子筛的制备，包括以下步骤：
称取16.22g的四丁基氢氧化铵置于去离子水中得到40wt％水溶液，在磁力搅拌下缓慢加入21.47g的正硅酸乙酯，待溶液澄清后加入38.87mL去离子水得到混合液；磁力搅拌6h后，加入0.12g柠檬酸铁和0.54g乙酰丙酮铜得到第一产物；磁力搅拌8h后将第一产物置于反应釜中在170℃条件下水热晶化72h；将晶化产物过滤和用去离子水反复洗涤，在100℃的干燥箱中干燥12h，得到第二产物，即全硅P-MEL@Cu/Fe分子筛；将0.015mol/L异丙醇铝和0.1mol/L四丁基氢氧化铵配置成有机碱处理液，然后取30mL的有机碱处理液与1g第二产物混合后置于反应釜中170℃水热条件下进行72h脱硅加铝，脱硅加铝结束后将产物过滤和用去离子水反复洗涤，在100℃的干燥箱中干燥12h，最后经过550℃煅烧6h，得到双金属MEL分子筛，即H-MEL@Cu/Fe分子筛。本发明实施例中，双金属MEL分子筛的硅铝比为48。
对实施例1制备得到的H-MEL@Cu/Fe分子筛进行表征分析。
采用德国Bruker公司的D8 Advance型X射线衍射仪对实施例1制备得到的H-MEL@Cu/Fe分子筛进行表征，结果请参阅图1，图1表明实施例1双金属MEL分子筛具有MEL沸石的特征衍射峰，且没有氧化铁和氧化铜结晶的杂峰存在。
采用日本Hitachi公司S-4800型冷场发射电子显微镜对实施例1制备得到的H-MEL@Cu/Fe分子筛进行表征，结果请参阅图2，图2表明实施例1双金属MEL分子筛形貌呈现类似橄榄球状结构。
采用日本电子的JEM-2100HR型200kV透射电子显微镜对实施例1制备得到的H-MEL@Cu/Fe分子筛进行表征，结果请参阅图3，图3表明实施例1双金属MEL分子筛形貌呈现出由片层堆积而成类似橄榄球状结构。
采用岛津Thermo Fisher Escalab 250Xi对实施例1制备得到的H-MEL@Cu/Fe分子筛检测铁和铜的存在形式，结果请参阅图4和图5，图4中，在～711.7eV和～725.3eV处分别观察到两个峰，对应于三价氧化态的Fe2p3/2和Fe 2p3/1。此外，在～716.5eV和～730.1eV处可以观察到Fe 2p的卫星峰是Fe2O3中Fe(III)的特征峰。图5中，在Cu 2p3/2和Cu 2p3/1峰在933.4eV和953.4eV归因于CuO，而Cu 2p3/2和Cu 2p3/1峰在～935.3eV和～955.3eV归因于Cu2+离子具有四面体配位。此外，卫星峰位于～972.7eV和～962.7eV是Cu2+物种的特征。图4和图5表明，在H-MEL@Cu/Fe分子筛中，Cu和Fe主要以配位形式存在。
BET吸附等温曲线通过N2吸附在-196℃下对实施例1制备得到的双金属MEL分子筛进行全孔分析，如图6所示，可以看出本发明的分子筛催化具有type-IV型回滞环说明存在微孔和介孔两种孔结构。图7和图8表明介孔的孔径为2nm～3.8nm，微孔的孔径为0.59nm以下。
实施例2
本实施例进行双金属MEL分子筛的制备，包括以下步骤：
称取16.22g的四丁基氢氧化铵置于去离子水中得到40wt％水溶液，在磁力搅拌下缓慢加入21.47g的正硅酸乙酯，待溶液澄清后加入38.87mL去离子水得到混合液；磁力搅拌6h后，加入0.25g柠檬酸铁和0.54g乙酰丙酮铜得到第一产物；磁力搅拌8h后将第一产物置于反应釜中在170℃条件下水热晶化72h；将晶化产物过滤和用去离子水反复洗涤，在100℃的干燥箱中干燥12h，得到第二产物，即全硅P-MEL@Cu/Fe分子筛；将0.015mol/L异丙醇铝和0.1mol/L四丁基氢氧化铵配置成有机碱处理液，然后取30mL的有机碱处理液与1g第二产物混合后置于反应釜中170℃水热条件下进行72h脱硅加铝，脱硅加铝结束后将产物过滤和用去离子水反复洗涤，在100℃的干燥箱中干燥12h，最后经过550℃煅烧6h，得到双金属MEL分子筛，即H-MEL@Cu/Fe分子筛。
本发明实施例中，双金属MEL分子筛的硅铝比为50，介孔的孔径为2nm～3.8nm，微孔的孔径为0.59nm以下。
对比例1
本对比例进行Fe金属MEL分子筛的制备，包括以下步骤：
称取16.22g的四丁基氢氧化铵置于去离子水中得到40wt％水溶液，在磁力搅拌下缓慢加入21.47g的正硅酸乙酯，待溶液澄清后加入38.87mL去离子水得到混合液；磁力搅拌6h后，加入0.25g柠檬酸铁得到第一产物；磁力搅拌8h后将第一产物置于反应釜中在170℃条件下水热晶化72h；将晶化产物过滤和用去离子水反复洗涤，在100℃的干燥箱中干燥12h，得到第二产物，即全硅P-MEL@Fe分子筛；将0.015mol/L异丙醇铝和0.1mol/L四丁基氢氧化铵配置成有机碱处理液，然后取30mL的有机碱处理液与1g第二产物混合后置于反应釜中170℃水热条件下进行72h脱硅加铝，脱硅加铝结束后将产物过滤和用去离子水反复洗涤，在100℃的干燥箱中干燥12h，最后经过550℃煅烧6h，得到Fe金属MEL分子筛，即H-MEL@Fe分子筛。
本发明实施例中，Fe金属MEL分子筛的硅铝比为47，介孔的孔径为2nm～3.8nm，微孔的孔径为0.59nm以下。
对比例2
本实施例进行双金属MEL微孔分子筛的制备，包括以下步骤：
称取16.22g的四丁基氢氧化铵置于去离子水中得到40wt％水溶液，在磁力搅拌下缓慢加入21.47g的正硅酸乙酯，待溶液澄清后加入38.87mL去离子水得到混合液；磁力搅拌6h后，加入0.25g柠檬酸铁和0.54g乙酰丙酮铜得到第一产物；磁力搅拌8h后将第一产物置于反应釜中在170℃条件下水热晶化72h；将晶化产物过滤和用去离子水反复洗涤，在100℃的干燥箱中干燥12h，得到第二产物，即全硅P-MEL@Cu/Fe分子筛。
本发明实施例中，双金属MEL分子筛的硅铝比为Si/Al＝∞，双金属MEL微孔分子筛只具有微孔，微孔孔径为～0.59nm。
实施例4
本实施例以三甲苯和苯甲醇的傅-克烷基化对实施例1～2双金属MEL分子筛和对比例1Fe金属MEL分子筛以及对比例2双金属MEL分子筛进行催化性能评价。
将装有回流冷凝器的三口圆底烧瓶在温控油浴锅中进行催化性能测试，首先，将40mmol的均三甲苯和0.1g MEL分子筛混合，并在100℃下保持搅拌0.5h，然后加入4mmol苯甲醇，以加入时间作为初始反应时间。最后，取出反应液通过气相色谱仪分析产物。苯甲醇的转化率和烷基化产物的选择性见表1，表1表明，本发明双金属MEL分子筛催化剂活性和选择性优于只负载铁的分子筛及只具有微孔的双金属MEL分子筛，本发明双金属MEL分子筛催化剂活性和选择性俱佳。
表1实施例1～2双金属MEL分子筛和对比例1Fe金属MEL分子筛以及对比例2双金属MEL分子筛催化下的苯甲醇的转化率和烷基化产物的选择性
| 分子筛 | 苯甲醇转化率(％) | 2-苄基-1，3，5-三甲基苯选择性(％) |
| 实施例1 | 54.11 | 92.32 |
| 实施例2 | 83.27 | 62.09 |
| 对比例1 | 33.28 | 36.94 |
| 对比例2 | 10.28 | 18.97 |
其中，
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种双金属MEL分子筛，其特征在于，所述双金属MEL分子筛具有介孔和微孔，所述介孔和所述微孔内负载有Cu和Fe；
所述双金属MEL分子筛的硅铝比为48～50。
2.根据权利要求1所述的双金属MEL分子筛，其特征在于，所述介孔的孔径为2nm～3.8nm，所述微孔的孔径为0.59nm以下。
3.权利要求1或2所述双金属MEL分子筛的制备方法，其特征在于，包括以下步骤：
a)将硅源、模板剂、铁源、铜源和去离子水混合，得到第一产物；
b)将所述第一产物进行晶化，得到第二产物；
c)将所述第二产物在含有铝源的有机碱处理液中水热条件下进行脱硅加铝，再依次进行干燥和焙烧，得到双金属MEL分子筛。
4.根据权利要求3所述的制备方法，其特征在于，步骤a)所述硅源选自正硅酸乙酯、气相二氧化硅和硅胶中的一种或多种；
所述模板剂选自四丁基氢氧化铵、四乙基氢氧化铵和四丙基氢氧化铵中的一种或多种；
所述铁源为有机配体铁，所述铜源为有机配体铜。
5.根据权利要求4所述的制备方法，其特征在于，所述硅源、所述模板剂、所述铁源、所述铜源和所述去离子水的摩尔比为1:0.25：(0.005～0.015)：0.02：(20～30)。
6.根据权利要求3所述的制备方法，其特征在于，步骤b)所述晶化的温度为165℃～170℃；
所述晶化的时间为72h～96h。
7.根据权利要求3所述的制备方法，其特征在于，步骤c)所述脱硅加铝的温度为165℃～170℃，所述脱硅加铝的时间为72h～96h；
所述焙烧的温度为500℃～550℃，所述焙烧的时间为5h～6h。
8.权利要求1或2所述双金属MEL分子筛和/或权利要求3至7任意一项所述制备方法制得的双金属MEL分子筛作为催化剂的应用。
9.根据权利要求8所述的应用，其特征在于，所述催化剂为傅-克烷基化反应催化剂。
10.根据权利要求9所述的应用，其特征在于，所述傅-克烷基化反应的反应底物为三甲苯和苯甲醇。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517050A (zh) * | 2021-01-06 | 2021-03-19 | 南京大学 | 一种包覆活性双金属氧化物的中空囊泡型介孔分子筛催化剂及其制备方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150147269A1 (en) * | 2012-06-08 | 2015-05-28 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Metal silicoaluminophosphate molecular sieve with rho framework structure, and method for preparing the same |
| CN106145143A (zh) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | 一种合成杂原子微介孔复合材料的方法 |
| CN108002402A (zh) * | 2017-12-08 | 2018-05-08 | 西北大学 | 一种具有千层饼状形貌的中微双孔mfi型纳米分子筛及其制备方法和应用 |
| CN108940356A (zh) * | 2018-05-29 | 2018-12-07 | 广东工业大学 | 一种Fe@ZSM-11介孔分子筛催化剂的制备方法 |
| CN109382137A (zh) * | 2018-11-14 | 2019-02-26 | 福州大学 | 一种介孔Fe-Cu-SSZ-13分子筛的制备方法及应用 |
-
2019
- 2019-09-18 CN CN201910883483.7A patent/CN110560146A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150147269A1 (en) * | 2012-06-08 | 2015-05-28 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Metal silicoaluminophosphate molecular sieve with rho framework structure, and method for preparing the same |
| CN106145143A (zh) * | 2015-04-17 | 2016-11-23 | 中国石油化工股份有限公司 | 一种合成杂原子微介孔复合材料的方法 |
| CN108002402A (zh) * | 2017-12-08 | 2018-05-08 | 西北大学 | 一种具有千层饼状形貌的中微双孔mfi型纳米分子筛及其制备方法和应用 |
| CN108940356A (zh) * | 2018-05-29 | 2018-12-07 | 广东工业大学 | 一种Fe@ZSM-11介孔分子筛催化剂的制备方法 |
| CN109382137A (zh) * | 2018-11-14 | 2019-02-26 | 福州大学 | 一种介孔Fe-Cu-SSZ-13分子筛的制备方法及应用 |
Non-Patent Citations (1)
| Title |
|---|
| JIAJIN HUANG等: ""Fabrication of Cu-Encapsulated Hierarchical MEL Zeolites for Alkylation of Mesitylene with Benzyl Alcohol"", 《INDUSTRIAL ENGINEERING CHEMISTRY RESEARCH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112517050A (zh) * | 2021-01-06 | 2021-03-19 | 南京大学 | 一种包覆活性双金属氧化物的中空囊泡型介孔分子筛催化剂及其制备方法和应用 |
| CN112517050B (zh) * | 2021-01-06 | 2021-11-30 | 南京大学 | 一种包覆活性双金属氧化物的中空囊泡型介孔分子筛催化剂及其制备方法和应用 |
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