CN113976181B - 一种钴基金属有机框架固载有机催化剂的制备及在燃油脱硫领域的应用 - Google Patents
一种钴基金属有机框架固载有机催化剂的制备及在燃油脱硫领域的应用 Download PDFInfo
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Abstract
本发明涉及一种钴基金属有机框架固载有机催化剂的制备及在燃油脱硫领域的应用，采用钴源六水合硝酸钴与不同配体对苯二甲酸、2,5‑二羟基对苯二甲酸、2‑甲基咪唑水热反应或室温老化合成的钴基金属有机框架Co‑MOF、通过浸渍法将N‑羟基邻苯二甲酰亚胺固载到Co‑MOF的孔道结构或沉积附着在Co‑MOF表面形成微孔‑介孔催化剂，是具有高孔隙率、高比表面积的有机‑无机杂化材料，在活化氧气下对含有硫化物特别是芳香族硫化物的油相进行氧化脱硫制得脱硫油品，Co‑MOF作为载体和助催化剂提升NHPI的固载和催化性能，使催化剂易于回收、增强稳定性、循环性能，反应条件温和、相较于NHPI及与六水合硝酸钴构成的催化系统具有更为优异的氧化脱硫效果，满足深度脱硫和绿色化工需求。
Description
技术领域
本发明属于燃油脱硫技术领域，具体涉及钴基金属有机框架固载N-羟基邻苯二甲酰亚胺的制备及在燃油脱硫领域的应用。
背景技术
多相催化剂的使用寿命及循环性能一直是化学研究及工业催化的重要研究领域，且对于同一活性中心，选择不同的载体，在氧化活性或选择性上会有不同程度的改变。近年来，各种多相催化剂的设计包括浸渍负载，化学键价接等等，为提高催化剂使用寿命和循环性能提供了新的思路。
近年来，环境日益恶劣，其主要原因是是燃油燃烧产生的各种硫化合物，对人体健康和生态环境伤害极大，而世界各国针对这一问题发布了严格的标准，燃油中的硫含量是最重要的环保指标。传统的加氢脱硫需要在高温，高压和氢气的氛围下进行，而且对噻吩类硫化合物及其衍生物脱硫效果不佳。因此，氧化脱硫，萃取脱硫，吸附脱硫，生物脱硫等非加氢脱硫的方法得到了广泛关注，其中氧化脱硫因其高脱硫率、反应条件温和被视为最有发展潜力的脱硫方式之一。氧化脱硫通过将含硫化合物氧化成极性大的砜类物质，然后通过水或是其他极性溶剂将氧化产物萃取而出，从而实现与油品分离的目的。
N-羟基邻苯二甲酰亚胺NHPI是一种高活性的有机催化剂，可以在氧化剂存在下产生邻苯二甲酰胺氮氧自由基PINO·、PINO·具有较强的攫氢能力，单纯以NHPI作为均相催化剂时，尽管具有活性高，反应条件温和的优点，但存在催化剂不易分离、不能循环使用以及体系不易纯化等缺点，在需氧氧化反应后难以回收，现有技术中采用有交联聚苯乙烯CPS微球、交联共聚微球GMA/MMA等载体固载NHPI，但其固载率、稳定性、循环性和应用于氧化脱硫的催化活性不佳，难以应用于燃油脱硫领域。
发明内容
本发明的目的是针对现有技术的缺陷，提供一种钴基金属有机框架固载有机催化剂的制备及在燃油脱硫领域的应用，采用钴源与不同配体合成的钴基金属有机框架Co-MOF、浸渍固载有机催化剂N-羟基邻苯二甲酰亚胺(NHPI)、用于燃油氧化脱硫，Co-MOF作为载体和助催化剂提升NHPI的固载和催化性能，使催化剂易于回收、增强稳定性、循环性能，反应条件温和、满足深度脱硫和绿色化工需求。
本发明是通过如下的技术方案予以实现的：
一种钴基金属有机框架固载有机催化剂的制备，其制备方法为：通过浸渍法将N-羟基邻苯二甲酰亚胺(NHPI)固载到Co-MOF的孔道结构或沉积附着在Co-MOF表面形成微孔-介孔催化剂。
进一步地，所述Co-MOF由六水合硝酸钴、配体、反应液水热反应或室温老化、取出离心、洗涤、干燥制得，所述配体包括对苯二甲酸(PTA)、2,5-二羟基对苯二甲酸、2-甲基咪唑，所述反应液包括N,N-二甲基甲酰胺(DMF)、乙醇、甲醇、去离子水中的一种或多种。
进一步地，所述六水合硝酸钴与对苯二甲酸(PTA)的摩尔比为0.1-1：0.1-1，所述反应液包括N,N-二甲基甲酰胺(DMF)、乙醇，在100-150℃下水热反应20-50h，以乙醇洗涤，在60℃下干燥获得紫色Co-MOF粉末；
Co-MOF-1的具体制备步骤如下：
将六水合硝酸钴0.1-1mmol加入N,N-二甲基甲酰胺(DMF)中均匀搅拌至溶解，然后取对苯二甲酸(PTA)0.1-1mmol加入N,N-二甲基甲酰胺(DMF)中均匀搅拌至溶解，将两种溶液混合搅拌,倒入少量乙醇继续均匀搅拌后的混合物倒入聚四氟乙烯内衬并放入反应釜内，在100-150℃下反应20-50h，取出反应物后经离心、乙醇洗涤数次后放入干燥箱内，在60℃下干燥，最终得到紫色Co-MOF-1粉末。
进一步地，所述六水合硝酸钴与2,5-二羟基对苯二甲酸的摩尔比为1-5:3-15，所述反应液包括N,N-二甲基甲酰胺(DMF)、乙醇和去离子水，以甲醇洗涤，在100℃下干燥获得棕色Co-MOF粉末；
Co-MOF-2的具体制备步骤如下：
取2,5-二羟基对苯二甲酸1-5mmol与六水合硝酸钴3-15mmol溶解于混合溶剂，混合溶剂由N,N-二甲基甲酰胺(DMF)、乙醇和去离子水按质量比1:1:1混配而成，将均匀搅拌的混合溶液置于聚四氟乙烯内衬中并放入反应釜内，在100-150℃下反应20-50h，取出反应物后经离心，以N,N-二甲基甲酰胺(DMF)，甲醇各清洗数次，真空干燥箱100℃干燥,最终得到棕色Co-MOF-2粉末。
进一步地，所述六水合硝酸钴与2-甲基咪唑的的摩尔比为1-4:4-16，所述反应液为甲醇，室温老化20-40h，以甲醇洗涤，在100℃下干燥获得紫色Co-MOF粉末；
Co-MOF-3的具体制备步骤如下：
将六水合硝酸钴1-4mmol溶解在甲醇中以制备金属溶液，2-甲基咪唑4-16mmol溶解在甲醇中作为配体溶液，将配体溶液快速倒入金属溶液中，室温老化20-40h，得到紫色产物用甲醇洗涤数次，在真空干燥箱中100℃干燥,最终得到紫色Co-MOF-2粉末。
微孔-介孔催化剂的具体浸渍负载步骤为：取N-羟基邻苯二甲酰亚胺(NHPI)、Co-MOF混溶于乙醇中，搅拌烘干，多次浸渍均匀负载，所述微孔-介孔催化剂的负载量为10-40wt％。
一种钴基金属有机框架固载有机催化剂在燃油脱硫领域的应用，其应用方法为：取上述任一制得的微孔-介孔催化剂在活化氧气下对含有硫化物、包括但不限于燃油的油相、进行氧化脱硫制得脱硫油品并分离回收微孔-介孔催化剂。
进一步地，所述微孔-介孔催化剂、油相、油相中的硫含量比例为：(0.02-0.1)g：(10-50)mL：(10-1000)ppm，所述氧气流量为50-800cm-3/min，氧化脱硫反应温度为100-150℃，反应时间为3-10h，所述硫化物包括但不限于二苯并噻吩(DBT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)。
本发明的有益效果为：
(1)采用钴基金属有机框架Co-MOF浸渍固载有机催化剂N-羟基邻苯二甲酰亚胺(NHPI)，Co-MOF由钴源-六水合硝酸钴、包括对苯二甲酸(PTA)、2,5-二羟基对苯二甲酸、2-甲基咪唑的不同配体溶解于相应反应液中水热反应或室温老化、干燥制得，是具有高孔隙率、高比表面积的有机-无机杂化材料，Co-MOF作为载体固载NHPI，通过简单的过滤离心即可回收，且有较为优异的稳定性及循环性能，制备过程简单，材料成本低廉，解决NHPI在需氧氧化反应后难以回收的问题；
(2)将Co-MOF固载NHPI的微孔-介孔催化剂在活化氧气下对含有硫化物、包括但不限于燃油的油相、进行氧化脱硫制得脱硫油品，相较于单纯的NHPI及与六水合硝酸钴构成的催化系统，Co-MOF作为助催化剂使微孔-介孔催化剂具有更为优异的氧化脱硫效果，满足深度脱硫的标准，且氧化脱硫可在相对低温，常压下对燃油等油相中的多种硫化物、特别是芳香族硫化物进行有效脱除，反应条件温和、易于操作，符合绿色化工的发展理念。
附图说明
图1为实施例2中催化剂Co-MOF-1b@NHPI、Co-MOF-3b@NHPI的酸碱总量检测结果图。
具体实施方式
下面结合附图和实施例对本发明的具体实施方式作进一步说明。
以下实施例所使用的燃油类型：
模型油品的配制：将二苯并噻吩(DBT)，和4,6-二甲基二苯并噻吩(4,6-DMDBT)分别溶解在十二烷中，DBT配成的油品硫含量10-1000ppm、4,6-DMDBT配成的油品硫含量10-1000ppm。
实施例1
一种钴基金属有机框架固载有机催化剂的制备，其制备方法为：
(1)选取不同的配体和钴源(六水合硝酸钴)合成不同的Co-MOF做载体：
Co-MOF-1(a,b,c)的合成：将六水合硝酸钴分别加入25mL的N,N-二甲基甲酰胺(DMF)中均匀搅拌至溶解获得DMF试剂，然后取对苯二甲酸(PTA)加入25mL的N,N-二甲基甲酰胺(DMF)中均匀搅拌至溶解，将相应比例的两种溶液分别混合搅拌5min,搅拌后的混合溶液分别加入乙醇，混合溶液与乙醇的体积比为4:1，继续均匀搅拌后的混合物倒入100mL的聚四氟乙烯内衬并放入反应釜内反应，取出反应物后经离心、乙醇洗涤数次后放入干燥箱内，在60℃下干燥，最终得到紫色Co-MOF-1粉末；
Co-MOF-2(a,b,c)的合成：取2,5-二羟基对苯二甲酸与六水合硝酸钴溶解于90mL混合溶剂，混合溶剂由N,N-二甲基甲酰胺(DMF)、乙醇和去离子水按体积比1:1:1混配而成，将均匀搅拌30min的混合溶液置于100mL的聚四氟乙烯内衬中并放入反应釜内，在100-150℃下反应20-50h，取出反应物后经离心，以N,N-二甲基甲酰胺(DMF)，甲醇各清洗数次，真空干燥箱100℃干燥,最终得到棕色Co-MOF-2粉末；
Co-MOF-3(a,b,c)的合成：将六水合硝酸钴溶解在25mL甲醇中以制备金属溶液，2-甲基咪唑溶解在甲醇中作为配体溶液，将配体溶液快速倒入金属溶液中，室温老化，得到紫色产物用甲醇洗涤数次，在真空干燥箱中100℃干燥,最终得到紫色Co-MOF-2粉末
各Co-MOF的具体合成条件如下表1：
(2)取N-羟基邻苯二甲酰亚胺(NHPI)、Co-MOF(-1，-2，-3)混溶于乙醇中，搅拌烘干，多次浸渍均匀负载，获得负载量为10％wt的微孔-介孔催化剂Co-MOF-1@NHPI，负载量为20％wt的微孔-介孔催化剂Co-MOF-2@NHPI，负载量为10％wt的微孔-介孔催化剂Co-MOF-3@NHPI，按照顺序命名Co-MOF-1a@NHPI,Co-MOF-1b@NHPI,Co-MOF-1c@NHPI,Co-MOF-2a@NHPI,Co-MOF-2b@NHPI,Co-MOF-2c@NHPI,Co-MOF-3a@NHPI,Co-MOF-3b@NHPI,Co-MOF-3c@NHPI。
实施例2
一种钴基金属有机框架固载有机催化剂在燃油脱硫领域的应用，其应用方法为：取实施例1任一制得的微孔-介孔催化剂0.07g用于有机硫化合物的脱除；
具体地：在有磁力搅拌的三颈烧瓶中，向20mL DBT(硫含量200ppm)模型油中加入催化剂，通入普通氧气100cm-3/min，在设定的温度下120℃磁力搅拌反应，反应持续4h，反应中催化剂和油品互不相溶，反应结束，取上层清油，离心，采用GC-FID(内标法，十六烷作为内标物，内标的浓度为4000ppm)测量硫含量，按照脱硫率％＝(1-油品中剩余硫含量/油品中硫总量)×100％，计算氧化脱硫效率，结果如下表2：
| 序号 | 油品 | 催化剂 | 反应时间/h | 脱硫率/％ |
| 1 | 模型油(DBT) | Co-MOF-1a@NHPI | 4 | 84 |
| 2 | 模型油(DBT) | Co-MOF-1b@NHPI | 4 | 85 |
| 3 | 模型油(DBT) | Co-MOF-1c@NHPI | 4 | 83 |
| 4 | 模型油(DBT) | Co-MOF-2a@NHPI | 4 | 98 |
| 5 | 模型油(DBT) | Co-MOF-2b@NHPI | 4 | 99 |
| 6 | 模型油(DBT) | Co-MOF-2c@NHPI | 4 | 97 |
| 7 | 模型油(DBT) | Co-MOF-3a@NHPI | 4 | 23 |
| 8 | 模型油(DBT) | Co-MOF-3b@NHPI | 4 | 21 |
| 9 | 模型油(DBT) | Co-MOF-3c@NHPI | 4 | 24 |
材料的酸碱性差异决定了活性的有无。酸碱总量由TPD-CO2，TPD-NH3测得，结果如附图1所示，图中a:Co-MOF-1b@NHPI的NH3-TPD；b:Co-MOF-3b@NHPI的NH3-TPD；c:Co-MOF-3b@NHPI的CO2-TPD。
实施例3
一种钴基金属有机框架固载有机催化剂在燃油脱硫领域的应用，其应用方法为：取实施例1制得的微孔-介孔催化剂Co-MOF-2c@NHPI0.06 g用于有机硫化合物的脱除；
具体地：在有磁力搅拌的三颈烧瓶中，向30mL 4,6-DMDBT(硫含量400ppm)模型油中加入催化剂Co-MOF-2c@NHPI，通入普通氧气300cm-3/min，在设定的温度下130℃磁力搅拌反应，反应持续8h，反应中催化剂和油品互不相溶，反应结束，取上层清油，离心，采用GC-FID(内标法，十六烷作为内标物，内标的浓度为4000ppm)测量硫含量，按照脱硫率％＝(1-油品中剩余硫含量/油品中硫总量)×100％，计算氧化脱硫效率，对于4,6-DMDBT的脱除率高达99％。
实施例4
一种钴基金属有机框架固载有机催化剂在燃油脱硫领域的应用，其应用方法为：取实施例1制得的微孔-介孔催化剂Co-MOF-2b@NHPI0.06 g用于有机硫化合物的脱除；
具体地：在有磁力搅拌的三颈烧瓶中，向20mL DBT(硫含量200ppm)模型油中加入催化剂Co-MOF-2b@NHPI，通入普通氧气200cm-3/min，在设定的温度下130℃磁力搅拌反应，反应持续8h，反应中催化剂和油品互不相溶，反应结束，取上层清油，离心，采用GC-FID(内标法，十六烷作为内标物，内标的浓度为4000ppm)测量硫含量，按照脱硫率％＝(1-油品中剩余硫含量/油品中硫总量)×100％，计算氧化脱硫效率；
催化剂与油品通过简单倾倒法分离，催化剂在普通氧气200cm-3/min、130℃下循环时间维持6h,反应结束，催化剂循环使用十次处理20mL DBT(硫含量200ppm)模型油，脱硫率如下表3：
综上，催化剂制备过程简单，材料成本低廉，解决了N-羟基邻苯二甲酰亚胺(NHPI)在需氧氧化反应后难以回收的问题，采用钴源与不同配体合成的钴基金属有机框架Co-MOF、浸渍固载有机催化剂N-羟基邻苯二甲酰亚胺(NHPI)、用于燃油氧化脱硫，Co-MOF作为载体和助催化剂提升NHPI的固载和催化性能，催化剂通过简单的过滤离心即可回收，且有较为优异的稳定性及循环性能、反应条件温和、满足深度脱硫和绿色化工需求。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围内。因此，本发明的保护范围应该以权利要求书的保护范围为准。
Claims (4)
1.一种钴基金属有机框架固载有机催化剂在燃油脱硫领域的应用，其特征在于，该有机催化剂在活化氧气下对含有硫化物的燃油油相进行氧化脱硫，制得脱硫油品；所述硫化物包括二苯并噻吩(DBT)；
所述有机催化剂的制备方法为：通过浸渍法将N-羟基邻苯二甲酰亚胺（NHPI）固载到Co-MOF的孔道结构或沉积附着在Co-MOF表面形成微孔-介孔催化剂；
所述Co-MOF由六水合硝酸钴、配体、反应液水热反应、取出离心、洗涤、干燥制得；所述配体为2,5-二羟基对苯二甲酸；
所述六水合硝酸钴与2,5-二羟基对苯二甲酸的摩尔比为1-5:3-15，所述反应液包括N,N-二甲基甲酰胺（DMF）、乙醇和去离子水，以甲醇洗涤，在100℃下干燥获得棕色Co-MOF粉末。
2.根据权利要求1所述的应用，其特征在于，取N-羟基邻苯二甲酰亚胺（NHPI）、Co-MOF混溶于乙醇中，搅拌烘干，多次浸渍均匀负载，所述微孔-介孔催化剂的负载量为10-40wt%。
3.根据权利要求1所述的应用，其特征在于，所述微孔-介孔催化剂、油相、油相中的硫含量比例为：（0.02-0.1）g：（10-50）mL：（10-1000）ppm。
4.根据权利要求1所述的应用，其特征在于，氧气流量为50-800 cm³/min，氧化脱硫反应温度为100-150℃，反应时间为3-10h。
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