CN105536864B - 具有核壳结构特征的zsm-5/eu-1复合分子筛的制备方法 - Google Patents
具有核壳结构特征的zsm-5/eu-1复合分子筛的制备方法 Download PDFInfo
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 47
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- 238000009825 accumulation Methods 0.000 description 1
- 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 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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- C07C2529/00—Catalysts comprising molecular sieves
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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- C07—ORGANIC CHEMISTRY
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- C07C2529/00—Catalysts comprising molecular sieves
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- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- C07—ORGANIC CHEMISTRY
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract
一种具有核壳结构特征的ZSM‑5/EU‑1复合分子筛的制备方法,是将硅源、铝源、模板剂、氢氧化钠加入水中形成均匀的凝胶液,并在凝胶液中加入柠檬酸,调节凝胶液的pH值为10.5~11.5,于140~200℃下晶化反应1~4天,将产物焙烧除去模板剂后以酸溶液离子交换,焙烧后得到氢型ZSM‑5/EU‑1复合分子筛,合成复合分子筛的原料用量满足Na2O∶SiO2∶Al2O3∶四丙基溴化铵∶溴化六甲双铵∶柠檬酸∶H2O=(0.01~0.05)∶(0.01~0.05)∶(0.0001~0.0005)∶(0.0001~0.001)∶(0.001~0.01)∶(0.5~1)∶(0.01~0.15)的摩尔比。
Description
技术领域
本发明涉及复合分子筛,特别是涉及一种ZSM-5/EU-1复合分子筛的制备方法。以本发明方法制备的复合分子筛结构特殊,且制备周期较短。
背景技术
将两种不同种类的分子筛复合在一起,可以表现出优于单一分子筛的催化性能。核壳型沸石分子筛作为复合分子筛中的一种特殊结构,是目前合成分子筛研究的一大热点。核壳分子筛的核相与壳相之间采用化学或物理作用紧密相连,不仅缩短了两种分子筛的扩散距离,还增强了两种分子筛的协同作用;核壳分子筛不但保留了组成分子筛的特性,同时还具有多种活性中心和双重孔道结构。因此,核壳分子筛在石油化工及精细化工领域有着广阔的应用前景。
当前核壳分子筛的合成方法基本为二次合成法。孔德金等采用两步晶化法,先将核相分子筛经柠檬酸、有机胺溶液、聚二烯丙基二甲基氯化铵(PDDA)等预先处理,改变核相分子筛表面电荷及酸性等性质,之后再将其加入到壳层生长合成液中继续晶化,在核相表面外延或者包覆生长一层壳相分子筛,所形成的核壳分子筛在催化反应中表现出了优于单一分子筛的催化性能(物理化学学报, 2009, 25(9), 1921.;Microporous andMesoporous Materials, 2009, 119, 91.;化学反应工程与工艺, 2011, 27(5), 385.)。虽然预处理剂在核壳分子筛合成中起到了关键的促进作用,但这些合成方法周期都比较长,且工序繁琐,在工业应用中具有一定的局限性。
双模板剂一步法合成复合分子筛可以有效解决这一问题,同时,通过添加一定量的预处理剂,也可以适当促进核壳结构的形成。但是,目前还未见采用类似方法合成具有工业应用价值的核壳结构催化剂材料的报道。
采用双模板剂一步法合成B-EU-1/ZSM-5复合分子筛(新型化工材料, 2015, 2,123.)的合成方法绿色简洁,成本较低。同样采用上述方法,利用ZSM-5和EU-1分子筛都具有十元环孔道结构的共同特征及催化优势,在合成过程中加入适量预处理剂柠檬酸,合成具有较合理分布酸性质、孔道性质的核壳结构复合分子筛ZSM-5/EU-1,可使其在甲醇转化反应中表现出良好的催化性能。
发明内容
本发明的目的是提供一种具有核壳结构特征的ZSM-5/EU-1复合分子筛的制备方法,通过一步晶化快速合成复合分子筛,以在甲醇转化制芳烃中表现出良好的催化活性。
本发明所述具有核壳结构特征的ZSM-5/EU-1复合分子筛中同时存在EU-1、ZSM-5分子筛两种晶相,且EU-1沿着ZSM-5表面缺陷处外延生长,形成核壳共生结构,所述复合分子筛具有微孔-介孔多级孔道,NH3-TPD测定强酸与弱酸峰面积比为1.2~1.6,采用下述方法制备得到:将合成分子筛所需的硅源、铝源、模板剂、氢氧化钠加入水中形成均匀的凝胶液,并在凝胶液中加入柠檬酸,调节凝胶液的pH值为10.5~11.5,于140~200℃下晶化反应1~4天,得到钠型ZSM-5/EU-1复合分子筛;将钠型ZSM-5/EU-1复合分子筛焙烧除去模板剂,以酸溶液进行离子交换,焙烧后得到氢型ZSM-5/EU-1核壳结构复合分子筛。其中,所述模板剂为四丙基溴化铵(TPABr)与溴化六甲双铵(HMBr2)的双模板剂,用于合成复合分子筛的各种原料的用量满足Na2O∶SiO2∶Al2O3∶四丙基溴化铵∶溴化六甲双铵∶柠檬酸∶H2O=(0.01~0.05)∶(0.01~0.05)∶(0.0001~0.0005)∶(0.0001~0.001)∶(0.001~0.01)∶(0.5~1)∶(0.01~0.15)的摩尔比。
本发明中,所述的硅源为硅溶胶、水玻璃、白炭黑中的一种,所述的铝源为十八水硫酸铝或偏铝酸钠。
本发明优选在90℃下,以0.1mol/L硝酸铵溶液对所述制备的钠型ZSM-5/EU-1复合分子筛进行离子交换。
本发明需要在离子交换前后分别对分子筛进行焙烧,并控制焙烧温度在350~650℃。
本发明上述制备方法中,所述的晶化时间优选为1~4天。
进一步地,本发明所述ZSM-5/EU-1复合分子筛中,所述EU-1分子筛不均匀的生长在ZSM-5分子筛周围,并在ZSM-5表面不同方向生长。
以甲醇为原料,使用上述制备的氢型ZSM-5/EU-1复合分子筛为催化剂,在压力0.1~5Mpa、温度300~460℃,原料液体空速0.1~5h-1条件下,进行甲醇转化制芳烃反应。得到的转化产物中以芳烃为主,且芳烃分布中以二甲苯为主,二甲苯中又以对二甲苯为主。
本发明采用双模板剂一步法,并在添加适量柠檬酸的条件下晶化合成ZSM-5/EU-1复合分子筛,采用XRD、SEM、TEM、N2吸附-脱附、NH3-TPD等手段对其进行表征,结果显示合成了具有较合理分布酸性质、孔道性质的核壳结构特征复合分子筛,分子筛中同时存在趋于立方结构的ZSM-5分子筛和球状颗粒的EU-1分子筛两种晶相,且EU-1在ZSM-5表面缺陷处外延生长;复合分子筛具有微孔-介孔多级孔道,微孔孔径相对于单一分子筛明显增大;复合分子筛的酸性相对单一分子筛有所改善,强酸量相对增强,催化活性进一步增强,有利于在催化反应中表现出较长的寿命和较高的催化活性,可使其在甲醇转化制芳烃反应中表现出良好的催化性能。
附图说明
图1为实施例1制备的ZSM-5/EU-1核壳分子筛的XRD谱图。
图2为实施例1制备的ZSM-5/EU-1核壳分子筛的SEM及TEM照片。
图3为实施例1制备的ZSM-5/EU-1核壳分子筛的吸附等温线图及孔径分布图。
图4为实施例1制备的ZSM-5/EU-1核壳分子筛的酸性分布图。
具体实施方式
下述实施例仅为本发明的优选技术方案,并不用于对本发明进行任何限制。对于本领域技术人员而言,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
实施例1
称取2g氢氧化钠、0.2g四丙基溴化铵、3g溴化六钾双铵、0.5g十八水硫酸铝,加入5mL去离子水,搅拌使其充分溶解,滴加5.465mol/L硅溶胶溶液10mL,待溶液呈凝胶状态后,继续加入0.1g柠檬酸,搅拌下调节凝胶液的pH值为10.5~11.5,转移至带聚四氟乙烯内衬的反应釜中,于180℃下静置晶化3天,取出,冷却、洗涤、过滤、烘干,得到钠型ZSM-5/EU-1复合分子筛。
将得到的钠型ZSM-5/EU-1复合分子筛在90℃下以0.1mol/L硝酸铵溶液离子交换2小时,去离子水洗涤,再用0.1mol/L硝酸铵溶液在90℃下离子交换2小时,去离子水洗涤,过滤,先在烘箱中100℃烘干,再置于马弗炉中500℃焙烧4小时,得到氢型ZSM-5/EU-1复合分子筛目标产物。
图1是ZSM-5分子筛、EU-1分子筛,以及本实施例制备的ZSM-5/EU-1复合分子筛的XRD谱图。从图中可以明显看到,ZSM-5/EU-1复合分子筛在2θ为7.8°、8.7°、23.2°、23.9°、24.4°(由■显示)处出现归属于ZSM-5的特征衍射峰,在2θ为7.8°、8.7°、19°、20.4°、22.1°(由●显示)处出现归属于EU-1的特征衍射峰,峰型尖锐且结晶度较高,说明在形成的复合分子筛中存在两种分子筛的晶相。
图2是本实施例制备的ZSM-5/EU-1复合分子筛的SEM、TEM照片。从图2(a)的SEM图片中观察到,采用一步法合成的复合分子筛的形貌为趋于立方结构的ZSM-5及球状颗粒的EU-1分子筛,EU-1分子筛沿ZSM-5表面缺陷处不均匀的外延生长在ZSM-5分子筛周围。且从图2(b)的TEM图中看出EU-1分子筛以ZSM-5表面缺陷处为成核中心外延生长,形成了核壳共生结构。图2(d)为图2(c)中A处的放大截图,高倍数放大以后,从图2(d)中B处可清晰的看到核壳分子筛排列有序的微孔孔道结构,而C处观察到的明纹,为晶粒堆积产生的介孔孔道,说明合成的复合分子筛为孔道融合度较高的微孔-介孔复合分子筛。
图3是本实施例1制备的ZSM-5/EU-1复合分子筛的N2吸附-脱附等温线及孔径分布图。从吸附-脱附等温线可看出,低压条件下的吸附量较高,且在相对压力为0.1时出现明显的回滞环,说明合成的复合材料为同时具有微孔-介孔的多级孔道复合分子筛。从孔径分布图可看出复合分子筛的微孔孔径主要分布在0.94nm左右,且在1.84nm附近也产生了明显的孔径堆积。由于复合以后EU-1侧袋的存在及柠檬酸加入后形成介孔孔道的协同作用,有利于催化反应中对二甲苯分子的扩散。
图4是以NH3-TPD测定的ZSM-5分子筛(a)、EU-1分子筛(b)、本实施例的ZSM-5/EU-1复合分子筛(c)的酸性拟合分布图。氢型分子筛的NH3-TPD图都显示两个吸收峰,其中低温吸收峰对应于分子筛的弱酸吸收峰,高温吸收峰对应于强酸吸收峰。可以看出,相比于H-ZSM-5分子筛,复合分子筛的低温、高温吸收峰分别降低了59℃、93℃,相比于H-EU-1分子筛,分别降低了10℃、20℃,说明正是因为核壳共生结构的形成,改变了铝在复合分子筛中的分布,合成液中加入的柠檬酸会破坏ZSM-5的结构,且有部分柠檬酸与溶液中的Al离子络合,导致铝含量减少,因此相应的酸强度也会减弱。根据拟合以后两个峰面积比即A(强酸)∶A(弱酸),H-EU-1为1.03,H-ZSM-5为0.95,H-ZSM-5/EU-1复合分子筛为1.59可知,合成的复合分子筛改善了单一分子筛的酸性质,强酸量有所提高,相对于单一分子筛的催化活性进一步增强,可在催化反应中表现出较长的寿命及催化效率。
实施例2
称取0.1g偏铝酸钠、0.08g柠檬酸、0.1g四丙基溴化铵、2.5g溴化六钾双铵溶于5mL去离子水中,澄清后滴加5.465mol/L硅溶胶溶液8mL搅拌均匀,加入1.5g氢氧化钠,搅拌至溶液呈凝胶状态后,调节凝胶液的pH值为10.5~11.5,转移至带聚四氟乙烯内衬的反应釜中,于170℃下静置晶化3天,取出,冷却、洗涤、过滤、烘干,500℃下焙烧得到钠型ZSM-5/EU-1复合分子筛。
取0.1g偏铝酸钠、0.08g柠檬酸及0.1gTPABr和2.5gHMBr2固体溶于5mL水中,澄清后滴加8ml 5.465mol/L硅溶胶,搅拌均匀,取1.5g氢氧化钠,搅拌至溶液呈凝胶态后调节pH为10.5~11.5并加入反应釜,于170℃下晶化3天,冷却、洗涤、抽滤、烘干,500℃下焙烧得到钠型复合分子筛。
将得到的钠型ZSM-5/EU-1复合分子筛在90℃下以0.1mol/L硝酸铵溶液离子交换2小时,去离子水洗涤,再用0.1mol/L硝酸铵溶液在90℃下离子交换2小时,去离子水洗涤,过滤,先在烘箱中100℃烘干,再置于马弗炉中500℃焙烧4小时,得到氢型ZSM-5/EU-1复合分子筛目标产物。
实施例3
向5mL去离子水中滴加4.36mol/L水玻璃10mL,再加入0.25g十八水硫酸铝,1.5g氢氧化钠,搅拌均匀,加入0.1g柠檬酸、0.3g四丙基溴化铵和2.5g溴化六钾双铵,搅拌至凝胶态,调节pH值为10.5~11.5,150℃晶化3天,冷却、洗涤、抽滤、烘干,500℃下焙烧得到钠型ZSM-5/EU-1复合分子筛。
将得到的钠型ZSM-5/EU-1复合分子筛在90℃下以0.1mol/L硝酸铵溶液离子交换2小时,去离子水洗涤,再用0.1mol/L硝酸铵溶液在90℃下离子交换2小时,去离子水洗涤,过滤,先在烘箱中100℃烘干,再置于马弗炉中500℃焙烧4小时,得到氢型ZSM-5/EU-1复合分子筛目标产物。
实施例4
称取0.05g柠檬酸、0.1g偏铝酸钠、0.25g四丙基溴化铵、2g溴化六钾双铵溶于5mL去离子水中,搅拌均匀,继续加入1g氢氧化钠,待溶液澄清后加入2g白炭黑,搅拌均匀并调节pH值为10.5~11.5,转移至带聚四氟乙烯内衬的不绣钢反应釜中,200℃下静置晶化2天,取出,冷却、洗涤、过滤、烘干,500℃焙烧得到钠型ZSM-5/EU-1复合分子筛。
将得到的钠型ZSM-5/EU-1复合分子筛在90℃下以0.1mol/L硝酸铵溶液离子交换2小时,去离子水洗涤,再用0.1mol/L硝酸铵溶液在90℃下离子交换2小时,去离子水洗涤,过滤,先在烘箱中100℃烘干,再置于马弗炉中500℃焙烧4小时,得到氢型ZSM-5/EU-1复合分子筛目标产物。
应用例
使用连续流动固定床反应器(内径10mm,长度30cm),对上述实施例1~4制备的氢型ZSM-5/EU-1复合分子筛催化剂进行甲醇芳构化反应评价。
将催化剂压片、破碎、筛分至20~40目,填装量2.5g。反应在390℃、0.5MPa、甲醇质量空速(WHSV)1.2h-1条件下进行。
反应后的液相产物经萃取分离,将芳烃与非芳烃分离,获得目标产物芳烃。
检测芳烃中各成分含量,计算二甲苯的选择性及二甲苯中对二甲苯的选择性。具体结果列于表1中。
Claims (5)
1.一种具有核壳结构特征的ZSM-5/EU-1复合分子筛的制备方法,所述ZSM-5/EU-1复合分子筛中同时存在EU-1、ZSM-5分子筛两种晶相,且EU-1沿着ZSM-5表面缺陷处外延生长,形成核壳共生结构,所述复合分子筛具有微孔-介孔多级孔道,NH3-TPD测定强酸与弱酸峰面积比为1.2~1.6,采用下述方法制备得到:将合成分子筛所需的硅源、铝源、模板剂、氢氧化钠加入水中形成均匀的凝胶液,并在凝胶液中加入柠檬酸,调节凝胶液的pH值为10.5~11.5,于140~200℃下晶化反应1~4天,得到钠型ZSM-5/EU-1复合分子筛;将钠型ZSM-5/EU-1复合分子筛焙烧除去模板剂,以酸溶液进行离子交换,焙烧后得到氢型ZSM-5/EU-1复合分子筛;其中,所述模板剂为四丙基溴化铵与溴化六甲双铵的双模板剂,用于合成复合分子筛的各种原料的用量满足Na2O∶SiO2∶Al2O3∶四丙基溴化铵∶溴化六甲双铵∶柠檬酸∶H2O=(0.01~0.05)∶(0.01~0.05)∶(0.0001~0.0005)∶(0.0001~0.001)∶(0.001~0.01)∶(0.5~1)∶(0.01~0.15)的摩尔比。
2.根据权利要求1所述的ZSM-5/EU-1复合分子筛的制备方法,其特征是所述的硅源为硅溶胶、水玻璃、白炭黑中的一种。
3.根据权利要求1所述的ZSM-5/EU-1复合分子筛的制备方法,其特征是所述的铝源为十八水硫酸铝或偏铝酸钠。
4.根据权利要求1所述的ZSM-5/EU-1复合分子筛的制备方法,其特征是所述的焙烧温度为350~650℃。
5.一种具有核壳结构特征的ZSM-5/EU-1复合分子筛的制备方法,所述ZSM-5/EU-1复合分子筛中同时存在EU-1、ZSM-5分子筛两种晶相,且EU-1沿着ZSM-5表面缺陷处外延生长,形成核壳共生结构,所述复合分子筛具有微孔-介孔多级孔道,NH3-TPD测定强酸与弱酸峰面积比为1.2~1.6,采用下述方法制备得到:将合成分子筛所需的硅源、铝源、模板剂、氢氧化钠加入水中形成均匀的凝胶液,并在凝胶液中加入柠檬酸,调节凝胶液的pH值为10.5~11.5,于140~200℃下晶化反应1~4天,得到钠型ZSM-5/EU-1复合分子筛;将钠型ZSM-5/EU-1复合分子筛焙烧除去模板剂,在90℃下,以0.1mol/L硝酸铵溶液对所述钠型ZSM-5/EU-1复合分子筛进行离子交换,焙烧后得到氢型ZSM-5/EU-1复合分子筛;其中,所述模板剂为四丙基溴化铵与溴化六甲双铵的双模板剂,用于合成复合分子筛的各种原料的用量满足Na2O∶SiO2∶Al2O3∶四丙基溴化铵∶溴化六甲双铵∶柠檬酸∶H2O=(0.01~0.05)∶(0.01~0.05)∶(0.0001~0.0005)∶(0.0001~0.001)∶(0.001~0.01)∶(0.5~1)∶(0.01~0.15)的摩尔比。
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