CN108033462B - 一种多级孔ltl分子筛及其合成方法和应用 - Google Patents
一种多级孔ltl分子筛及其合成方法和应用 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 67
- 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 67
- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 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
- 238000005406 washing Methods 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- 229920002593 Polyethylene Glycol 800 Polymers 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
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 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
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 3
- 239000002184 metal Substances 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 2
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 16
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 16
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- -1 C6-C8 alkane Chemical class 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Abstract
本发明公开了一种多级孔LTL分子筛及其合成方法和应用。所述LTL分子筛的制备方法包括如下步骤:(1)配制铝源和钾源的混合水溶液;(2)向所述混合水溶液中依次加入硅源和聚乙二醇水溶液,经老化得到筛初始溶胶混合物;(3)所述筛初始溶胶混合物依次经恒温晶化和焙烧即得。本发明多级孔LTL分子筛合成方法简单,合成过程无毒无害;本发明LTL分子筛具有多级孔结构,其中介孔集中在2~7nm;本发明多级孔LTL分子筛在正辛烷芳构化反应中表现出优异的催化性能,与传统微孔LTL催化剂相比,芳烃收率提高20%多,具有很好的工业应用前景。
Description
技术领域
本发明涉及一种多级孔LTL分子筛及其合成方法和应用,属于分子筛技术领域。
背景技术
芳烃作为基本的化工行业的原材料之一,在石油化工体系中占有极其重要的作用。LTL分子筛具有独特的择形性、较强的碱性中心及良好的水热稳定性,在C6~C8烷烃芳构化反应中表现出优异的催化性能。然而,一维十二元环孔道结构具有较大的扩散限制,生成的较高碳数芳烃(如二甲苯)由于不能及时扩散到孔道外会继续发生氢解等二次副反应,造成芳构化产物以苯和甲苯为主,降低了芳烃收率和液收;同时由于产物在一维孔道内的扩散限制,在催化反应中极易造成积碳而失活。通常而言,在微孔分子筛体系里引入介孔可以有效地提高反应物和产物的扩散速率,进而减少积碳的形成,提高目标产物收率和催化剂的寿命。因此,多级孔LTL分子筛的合成具有重要的研究价值。
近些年来,很多合成方法如后处理法、硬模板法和软模板法等已被成功应用于制备多级孔分子筛。其中对于LTL分子筛而言,Minkee Choi等研究者采用后处理的造孔方法,即先用乙二胺四乙酸脱铝再通过氢氧化钾脱硅的方法,对LTL分子筛构造晶间介孔(J.Catal.,66-75(2016)340),并通过多种模型化合物对处理后的分子筛进行性能评价,实验结果发现连续脱铝脱硅的方法可以引入二次介孔从而改善产物在分子筛孔道内的扩散性能,进而提高芳烃收率特别是碳八芳烃收率。但采用后处理的方法比较麻烦同时会产生较多的酸碱废液,限制了其在工业生产中的应用。因而寻求一种简单、高效并且廉价的方法制备具有高性能的多级孔分子筛具有极大的实际应用价值。
发明内容
本发明的目的是提供一种具有多级孔结构的LTL分子筛及其制备方法,所述LTL分子筛具有多级孔结构,平均晶体粒度尺寸为1μm左右,介孔尺寸主要集中在2~7nm之间,介孔体积为0.2cm3/g,比表面积高达350m2/g。
本发明多级孔结构LTL分子筛有利于提高反应物和产物在分子筛孔道内的扩散速率,避免二次副反应的发生,从而提高芳烃的收率。
本发明采用水热合成方法制备多级孔LTL分子筛,以水作为溶剂,通过添加价格低廉的聚乙二醇(PEG)聚合物,调变溶胶组成及浓度,在晶化反应釜内通过自生压力得到具有多级孔结构的LTL分子筛。
具体地,本发明方法包括如下步骤:
(1)配制铝源和钾源的混合水溶液;
(2)向所述混合水溶液中依次加入硅源和聚乙二醇水溶液,经老化得到初始溶胶混合物;
(3)所述初始溶胶混合物依次经恒温晶化和焙烧即得所述具有多级孔结构的LTL分子筛。
上述的制备方法中,所述铝源可为异丙醇铝、硝酸铝、氢氧化铝或拟薄水铝石;
所述钾源可为氢氧化钾;
所述硅源可为白炭黑、水玻璃、硅酸钠或硅溶胶。
上述的制备方法中,所述聚乙二醇可为PEG-200、PEG-400、PEG-600和PEG-800中至少一种;
所述钾源、所述硅源和所述铝源的量以其氧化物的量计,所述聚乙二醇、所述钾源、所述硅源、所述铝源和水的摩尔比可为0.1~8:0.5~6:3~15:1:300~600,具体可为1~2:2.56:11.30:1:375、1:2.56:11.30:1:375或2:2.56:11.30:1:375。
上述的制备方法中,步骤(1)中,所述方法还包括将所述混合水溶液于20~100℃条件下搅拌1~20h的步骤,如于90~100℃条件下搅拌10~12h。
上述的制备方法中,步骤(2)中,所述老化的温度可为10~50℃,时间可为1~10h,如在20℃下老化1~5小时。
上述的制备方法中,步骤(3)中,所述恒温晶化的温度可为120~180℃,时间可为20~48h,如在160~180℃的条件下恒温晶化24~48h、160℃的条件下恒温晶化24h、170℃的条件下恒温晶化48h或180℃的条件下恒温晶化48h。
上述的制备方法中,步骤(3)中,所述焙烧之前还包括依次进行的过滤、洗涤、干燥的步骤;
所述洗涤步骤将洗出液洗涤至中性,优选有去离子水洗涤;
所述干燥的温度可为80~130℃,时间可为1~12h;
所述焙烧的温度可为450~600℃,时间可为4~10h,可在氧气或空气中进行,通过所述焙烧去除原粉中所含的溶剂,从而得到具有多级孔结构的LTL分子筛。
本发明通过的制备方法简单,合成成本低廉,相比后处理方法而言,不需要后续的酸碱处理,极大地减少了合成成本以及所产生的废液污染。
本发明提供的多级孔LTL分子筛可广泛用作各种烃类转化的催化剂载体,尤其可用作C6~C8烷烃芳构化反应的催化剂载体。
本发明多级孔LTL分子筛在用于C6~C8构烷烃芳构化反应时,可通过浸渍法在所述多级孔LTL分子筛上负载适宜比例的催化活性组分后,即得到烷烃芳构化催化剂。
所述催化活性组分可以是Pt、Pd、Ir等中的任意一种或多种的组合。
具体地,例如,通过浸渍法将0.5wt.%Pt负载到上述分子筛载体上制得芳构化催化剂;在使用前,需要在反应前需要在空气气氛中120℃干燥12h,再在350℃下焙烧4h。
上述催化剂用于催化烷烃芳构化反应,如催化C6~C8烷烃的芳构化时,芳烃收率显著提高。
采用上述催化剂催化烷烃芳构化反应时,可在固定床反应器中进行,以正辛烷为例,所述烷烃芳构化反应的反应条件可为:正辛烷空速可为1~3h-1,氢气/正辛烷摩尔比可为0.2~6.0,反应压力可为0.1~2MPa,反应温度可为300~600℃
本发明具有以下优点:
1、本发明多级孔LTL分子筛合成方法简单,合成过程无毒无害;
2、本发明LTL分子筛具有多级孔结构,其中介孔集中在2~7nm;
3、本发明多级孔LTL分子筛在正辛烷芳构化反应中表现出优异的催化性能,与传统微孔LTL催化剂相比,芳烃收率提高20%多,具有很好的工业应用前景。
附图说明
图1为本发明对比例1制备的LTL分子筛的XRD谱图。
图2为本发明对比例1制备的LTL分子筛的SEM照片。
图3为本发明实施例1制备的LTL分子筛的XRD谱图。
图4为本发明实施例1制备的LTL分子筛的SEM照片。
图5为本发明实施例2制备的LTL分子筛的XRD谱图。
图6为本发明实施例2制备的LTL分子筛的SEM照片。
图7为本发明实施例3制备的LTL分子筛的XRD谱图。
图8为本发明实施例3制备的LTL分子筛的SEM照片。
图9为本发明实施例1、2、3制备的LTL分子筛的孔径分布图。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
下述实施例中所用的材料、试剂等,如无特殊说明,均可从商业途径得到。
对比例1、
取150.6g KOH、45.2g氢氧化铝加入到1400g去离子水中,搅拌均匀后转移至三口烧瓶中于80℃反应12h,冷却至室温后得到澄清KAlO2溶液,该铝源溶液中K2O:Al2O3的摩尔比为3.85:1。向该溶液中边搅拌边缓慢加入305.4g硅溶胶(SiO2含量30wt%),充分混合得到LTL分子筛溶胶,在20℃下陈化1h后转移至静态釜中于170℃下晶化24h。产物经去离子水洗涤至中性,然后在120℃干燥12h、于500℃焙烧4h后即可得到LTL分子筛原粉。
取部分样品做X-射线粉末衍射测定,图1为样品的XRD谱图,结果说明得到的产品为LTL分子筛;图2为样品的SEM照片,结果说明所制备样品均为圆柱状,平均晶体粒度尺寸为1μm左右,是典型的LTL拓扑结构分子筛形貌特征。氮气吸附测试的结果表明该样品的表面积为296m2/g。
实施例1、
取100.3g KOH、45.3g氢氧化铝加入到1300g去离子水中,搅拌均匀后转移至三口烧瓶中于90℃反应12h,冷却至室温后得到澄清KAlO2溶液,该铝源溶液中K2O:Al2O3的摩尔比为2.56:1。向该溶液中边搅拌边缓慢加入668g硅溶胶(SiO2含量30wt%),强力搅拌均匀后得到初始溶胶。取59.52g PEG200溶于200g去离子水中制成PEG溶液。将PEG溶液缓慢滴加进溶胶中继续强力搅拌,在20℃下陈化1h后转移至动态釜中,在170℃条件下反应48h。晶化结束后,将反应物冷却至室温,过滤、用去离子水洗至中性并在85℃干燥11h、于450℃焙烧10h后得到多级孔LTL沸石。
其中,氢氧化铝的量以Al2O3计,KOH的量以K2O计,硅溶胶的量以SiO2计,投料比(摩尔比)为:11.30SiO2:2.56K2O:1Al2O3:1PEG200:375H2O。
取部分样品做X-射线粉末衍射测定,图3为样品的XRD谱图,结果说明得到的产品为LTL分子筛;图4为样品的SEM照片,结果说明所制备样品均为圆柱状,颗粒大小在1μm左右,是典型的LTL拓扑结构分子筛形貌特征。氮气吸附测试的结果表明该样品具有更高的表面积,高达320m2/g。
实施例2、
取100.3gKOH、45.3g氢氧化铝加入到1200g去离子水中,搅拌均匀后转移至三口烧瓶中于100℃反应12h,冷却至室温后得到澄清KAlO2溶液,该铝源溶液中K2O:Al2O3的摩尔比为2.56:1。向该溶液中边搅拌边缓慢加入668g硅溶胶(SiO2含量30wt%),强力搅拌均匀后得到初始溶胶。取357.12g PEG600溶于300g去离子水中制成PEG溶液。将PEG溶液缓慢滴加进溶胶中继续强力搅拌,在20℃下陈化1h后转移至动态釜中,在180℃条件下反应48h。晶化结束后,将反应物冷却至室温,过滤、用去离子水洗至中性并在130℃干燥3h、于450℃焙烧6h后得到多级孔LTL沸石。
其中,氢氧化铝的量以Al2O3计,KOH的量以K2O计,硅溶胶的量以SiO2计,投料比(摩尔比)为:11.30SiO2:2.56K2O:1Al2O3:2PEG600:375H2O。
取部分样品做X-射线粉末衍射测定,图5为样品的XRD谱图,表明得到的产品为LTL分子筛;并且与对比例1相比,该样品XRD的峰出现宽化,表明分子筛晶粒尺寸有所减小。图6为样品的SEM照片,结果说明所制备样品均为纺锤状,是一种特殊的LTL拓扑结构分子筛形貌。氮气吸附测试的结果表明该样品的表面积为337m2/g。
实施例3、
取100.3gKOH、45.3g氢氧化铝加入到1100g去离子水中,搅拌均匀后转移至三口烧瓶中于90℃反应10h,冷却至室温后得到澄清KAlO2溶液,该铝源溶液中K2O:Al2O3的摩尔比为2.56:1。向该溶液中边搅拌边缓慢加入668g硅溶胶(SiO2含量30wt%),强力搅拌均匀后得到初始溶胶。取476.16g PEG800溶于400g去离子水中制成PEG溶液。将PEG溶液缓慢滴加进溶胶中继续强力搅拌,在20℃下陈化5h后转移至动态釜中,在160℃条件下反应24h。晶化结束后,将反应物冷却至室温,过滤、用去离子水洗至中性并在110℃干燥12h、于600℃焙烧4h后得到多级孔LTL沸石。
其中,氢氧化铝的量以Al2O3计,KOH的量以K2O计,硅溶胶的量以SiO2计,投料比(摩尔比)为:11.30SiO2:2.56K2O:1Al2O3:2PEG800:375H2O。
取部分样品做X-射线粉末衍射测定,图7为样品的XRD谱图,结果说明得到的产品为LTL分子筛,XRD峰的宽化表明分子筛晶粒尺寸有所减小;图8为样品的SEM照片,结果说明所制备样品均为球状,是一种特殊形貌的LTL分子筛。氮气吸附测试的结果表明该样品具有更高的表面积,高达354m2/g。
图9为本发明实施例1、2和3制备的样品的孔径分布曲线,其中位于0.7nm左右的孔道归属于LTL分子筛的十二元环孔道,而位于2.0~7.0nm左右的孔道归属于介孔孔道。
实施例4、反应性能评价
将实施例1-3制备的杂原子分子筛及对比例1中的LTL分子筛通过浸渍法负载0.5wt.%的Pt,然后在空气气氛中于120℃干燥12h,再在350℃焙烧4h制备相应催化剂。然后以正辛烷为原料,对其芳构化性能在固定床反应器中进行评价。
其中,质量空速(WHSV)为2h-1,氢烃比为7(摩尔比),反应压力为0.7MPa,反应温度为500摄氏度。其中液相产物经冷凝后离线分析,气相产物在线分析。
催化剂评价结果如下:
以该载体制备的催化剂在正辛烷芳构化反应中表现出优异的催化性能,如表1所示,可以看出,实施例3制备的催化剂在91.35%的转化率情况下,总芳烃收率达到66.58%,其中C8芳烃收率达到34.76%。而常规分子筛(对比例1)催化剂在转化率相近的情况下,总芳烃收率为44.21%,而C8芳烃收率仅为6.23%,远远低于本发明分子筛制备的催化剂的转化效果。
表1各催化剂的催化性能评价
从表1中的数据可以看出,本发明多级孔分子筛制备的催化剂在正辛烷芳构化反应中具有较高的芳烃收率和液收,特别是C8芳烃收率得到了明显提高。
Claims (7)
1.一种具有多级孔结构的LTL分子筛的制备方法,包括如下步骤:
(1)配制铝源和钾源的混合水溶液;
(2)向所述混合水溶液中依次加入硅源和聚乙二醇水溶液,经老化得到筛初始溶胶混合物;
所述聚乙二醇为PEG-200、PEG-400、PEG-600和PEG-800中至少一种;
所述钾源、所述硅源和所述铝源的量以其氧化物的量计,所述聚乙二醇、所述钾源、所述硅源、所述铝源和水的摩尔比为0.1~8:0.5~6:3~15:1:300~600;
所述老化的温度为10~50℃,时间为1~10h;
(3)所述初始溶胶混合物依次经恒温晶化和焙烧即得所述具有多级孔结构的LTL分子筛;
所述恒温晶化的温度为120~180℃,时间为20~48 h;
所述焙烧的温度为450~600℃,时间为4~10h。
2.根据权利要求1所述的制备方法,其特征在于:所述铝源为异丙醇铝、硝酸铝、氢氧化铝或拟薄水铝石;
所述钾源为氢氧化钾;
所述硅源为白炭黑、水玻璃、硅酸钠或硅溶胶。
3.根据权利要求1或2所述的制备方法,其特征在于:步骤(1)中,所述方法还包括将所述混合水溶液于20~100℃条件下搅拌1~20h的步骤。
4.根据权利要求3所述的制备方法,其特征在于:步骤(3)中,所述焙烧之前还包括依次进行的过滤、洗涤和干燥的步骤;
所述洗涤步骤将洗出液洗涤至中性;
所述干燥的温度为80~130℃,时间为1~12h。
5.权利要求1-4中任一项所述方法制备的具有多级孔结构的LTL分子筛。
6.一种以权利要求5所述具有多级孔结构的LTL分子筛为载体的催化剂;
所述具有多级孔结构的LTL分子筛上负载活性金属;
所述活性金属选自下述至少一种:Pt、Pd和Ir;
所述活性金属的质量负载量为0.1~2.0%。
7.权利要求6所述催化剂在催化烷烃芳构化反应中的应用。
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