CN112010726B - 一种催化纤维素选择性制备小分子烷烃的方法 - Google Patents
一种催化纤维素选择性制备小分子烷烃的方法 Download PDFInfo
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Abstract
本发明公开了一种催化纤维素选择性制备小分子烷烃的方法，在水和C10以上的烷烃组成的双相体系中，首次通过酸性脱水催化剂α‑ZrP和加氢脱氧催化剂(Ru‑MoOx/C)协同作用，将纤维素解聚产单糖反应和后续单糖的加氢脱氧反应耦合，一步法产C1‑C6烷烃和CO燃料，解决了现有技术步骤繁琐、催化剂循环性能差的问题。
Description
技术领域：
本发明涉及一种催化纤维素选择性制备小分子烷烃的方法。
背景技术：
在生物质中，纤维素是自然界中最丰富的生物质资源，其主要来源于植物和农林废弃物。可通过化学或生物手段应用于生产液体和气态燃料/汽油添加剂。其中，作为小分子烷烃燃料主要包含3种类型的烷烃，包括天然气(NG，C1-C2烷烃)，液化石油气(LPG，C3-C4烷烃)和汽油主要成分(GAS，C5-C6烷烃)。其中，C5-C6烷烃在常温常压下均为液态，这两种简单饱和烃在提高汽油辛烷值和调节汽油蒸汽压等方面不可缺。此外，纤维素在转化到小分子烷烃的过程中，还可以产生水煤气的主要成分，CO。现有绝大多数技术以HZSM-5分子筛耦合双金属催化剂对纤维素进行降解产小分子烷烃，存在液化石油气LPG产率较低、催化剂循环性能差以及转化路径不清楚等问题。
发明内容：
本发明的目的是提供一种催化纤维素选择性制备小分子烷烃的方法，在水和C10以上的烷烃组成的双相体系中，首次通过酸性脱水催化剂α-ZrP和加氢脱氧催化剂(Ru-MoOx/C)协同作用，将纤维素解聚产单糖反应和后续单糖的加氢脱氧反应耦合，一步法产C1-C6烷烃和CO燃料，解决了现有技术步骤繁琐、催化剂循环性能差的问题，并且为从生物质资源转化LPG提供了初步的借鉴思路。
本发明是通过以下技术方案予以实现的：
一种催化纤维素选择性制备小分子烷烃的方法，在水和C10以上的烷烃组成的双相体系中，加入酸性脱水催化剂α-ZrP和Ru-MoOx/C和纤维素，充入氢气，压力为5-7Mpa，反应温度为200-240℃，一步法产C1-C6烷烃和CO燃料。
优选地，α-ZrP和Ru-MoOx/C的质量比为0.05：0.2-0.15：0.2。
Ru-MoOx/C中，Ru和Mo负载量分别为3-5wt.％和10-20wt.％。
本发明的有益效果如下：首次运用酸性脱水催化剂α-ZrP耦合加氢脱氧催化剂(Ru-MoOx/C)协同催化纤维素产小分子烷烃，将纤维素解聚产单糖反应和后续单糖的加氢脱氧反应耦合，一步法产C1-C6烷烃和CO燃料，解决了现有技术步骤繁琐、催化剂循环性能差的问题，并且为从生物质资源生产液化石油气C3-C4烷烃提供初步探究思路。
附图说明：
图1是催化剂的SEM和TEM图；
其中，(a)为α-ZrP催化剂的SEM图，(b)-(c)为新鲜还原的5％Ru-10％MoOx/C催化剂的TEM图。
图2是催化剂的X射线衍射图：
其中(a)为α-ZrP催化剂，(b)为新鲜还原5％Ru-10％MoOx/C催化剂。
图3是新鲜还原的5％Ru-10％MoOx/C催化剂X射线光电子能谱(XPS)图；
其中(a)Ru物种，(b)Mo物种。
图4是新鲜还原的5％Ru-10％MoOx/C催化剂的Py-FTIR光谱图。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1：催化剂的制备及表征
将4.0gZrOCl2·8H2O与40.0mL(浓度为3.0M)H3PO4溶液混合，密封在装有内衬的水热釜中，在200℃下加热24h。反应结束后，混合物用去离子水通过0.22μmMillipore滤头过滤，直至滤液为中性。将固体产物在60℃下干燥过夜，获得2.4gα-ZrP。其SEM图参见图1(a)，可以看到α-ZrP六方纳米片的平均粒径和厚度分别为约288nm和20nm，代表α-ZrP的整体外观。α-ZrP的BET比表面积和孔径分布数据在图2(a)所示，在图2(a)中α-ZrP的氮气吸附-脱附等温曲线下凹，且没有拐点。吸附气体量随相对压力(P/P0)增加而上升，属于III型等温线。α-ZrP的BET比表面积为22.5m2/g，孔容为0.2cm3/g。就其孔径分布而言，原始α-ZrP的孔径为26.4nm，属于介孔(表1，目录1)。
表1 BET测量获得的催化剂的性能参数
a：Barret-Joyner-Halenda孔径分布
b：t-曲线微孔容，Horvath-Kawazoe中值孔径
采用分步浸渍法制备Ru-MoOx/C催化剂。具体实验步骤为，首先将活性炭在110℃下用HNO3溶液(0.6mol·L-1)预处理5h，然后室温下过滤直至中性，并在100℃烘箱中干燥过夜。将RuCl3·3H2O溶解于去离子水中，并根据Ru的负载量(wt.％)中加入一定量的活性炭，并在室温下搅拌4h。将固体在100℃干燥过夜，并在流动的氮气气氛(35mL·min-1)中，400℃煅烧4h。在制备Ru/C催化剂好后，用(NH4)6Mo7O24溶液，通过与上述相同的方法进行第二次浸渍，制备含有不同Ru和Mo负载量的Ru-MoOx/C催化剂(标记为3％Ru-20％MoOx/C，5％Ru-10％MoOx/C)。在实验之前，将煅烧过样品在350℃的流动氢气(35mL·min-1)中还原4h。5％Ru-10％Mox/C的TEM图参见图1中(b)-(c)，在图1(b)的TEM图中，通过FFT法计算可知其晶面间距d约为1nm的MoO2颗粒。在图1(c)的TEM中，可发现催化剂表面存在两种类型颗粒，对比可知粒径较大者为MoOx，而粒径较小者则为Ru0颗粒，并且在该视界内的MoOx颗粒通过FFT法计算可知，其为晶面间距d为0.6nm的MoO3颗粒。通过以上TEM分析，得知Ru-MoOx/C组分包括负载于活性碳上的Ru0，MoO2以及MoO3(MoO2和MoO3为MoOx组分)。
5％Ru-10％Mox/C的BET比表面积和孔径分布数据的分别在图2(b)所示。图2(b)中显示Ru-MoOx/C样品的氮气吸附-脱附等温曲线，在较低的P/P0下显示较高的氮气吸收量，该等温线属于I型等温线。Ru-MoOx/C催化剂的孔径属于杂多孔类型，包含微孔(<2nm)和中孔(2-15nm)。比表面积为784.4m2/g，孔容为0.27cm3/g，孔径为0.61nm(参见表1，目录2)。
新鲜还原的5％Ru-10％MoOx/C催化剂X射线光电子能谱(XPS)图参见图3。在图3(a)关于Ru物种的XPS谱图中，由于Ru3d和C1s结合能区域之间的重叠严重，因此很难通过Ru3d区域的结合能分析Ru的状态。但是，结合能在约483.7和461.2eV处分别表示金属Ru0的Ru3p3/2和Ru3p1/2峰。通过以上分析说明，钌钼碳催化剂中Ru都已完全被还原为金属状态。在图3(b)关于Mo物种的XPS谱图中，纯净MoO3的XPS光谱显示在结合能232.5eV(Mo3d5/2)和235.6eV(Mo3d3/2)处存在两条分辨较好的谱线，而纯净的MoO2由232.6eV(Mo3d3/2)和229.8eV(Mo3d5/2)两条谱线组成。氧空位可以来源于MoO2和MoO3，并且氧空位缺陷作为电子受体可以产生Lewis酸位点。因此，Ru-MoOx/C上的MoOx组分是该催化剂Lewis酸位点的来源。
图4是5％Ru-10％Mox/C催化剂的Py-FTIR光谱：波长位于1450、1576和1600cm-1处的谱带，分别对应于吡啶在强Lewis酸，弱Lewis酸以及强Lewis酸上的吸附位点，而1489cm-1附近的波段则归因于
酸位点和Lewis酸位点的重叠峰。通过分析计算得到该催化剂的Lewis酸总量为22.6μmol/g。说明Ru-MoOx/C酸性主要以Lewis酸性形式存在。
实施例2：α-ZrP耦合Ru-MoOx/C用于催化纤维素制备小分子烷烃
在水和正癸烷(n-decane)组成的双相体系中，加入实施例1制备的酸性脱水催化剂α-ZrP和Ru-MoOx/C，加入纤维素，充入氢气，压力为6Mpa，反应温度为200-240℃，一步法产C1-C6烷烃和CO燃料。具体反应参数及结果参见表2。
表2α-ZrP耦合Ru-MoOx/C用于催化纤维素制备小分子烃烷
反应条件：
a：0.1gα-ZrP，0.2g5％Ru-10％MoOx/C，0.25g纤维素，T＝200℃,p(H2)＝6Mpa,t＝18h
b：0.1gα-ZrP，0.2g3％Ru-20％MoOx/C，0.25g纤维素，T＝240℃,p(H2)＝6Mpa,t＝18h
c：0.1gα-ZrP，0.2g3％Ru-20％MoOx/C，0.25g纤维素，T＝240℃,p(H2)＝6Mpa,t＝18h
液相产物中主要产物为葡萄糖Glu，山梨糖醇Sor，甘油Sor，乙二醇EG，1，2-丙二醇PDO，异丙醇ISP，丙醇Pro，乙醇Eth以及甲醇Met。从表2中得知：在m纤维素＝0.25g，mα-ZrP＝0.1g，mRu-MoOx/C＝0.2g情况下，当水和n-decane的体积比VA/VO＝9/18时，在T＝200℃，p(H2)＝6Mpa，t＝18h作用下，在5％Ru-10％MoOx/C作用下气相中CO和C1-C4烷烃(包括NG和LPG，下同)产率分别为1.3％和34％，有机相中C5-C6烷烃产率分别为46.3％；在T＝240℃，p(H2)＝6Mpa，t＝18h作用下，在3％Ru-20％MoOx/C作用下气相中CO和C1-C4烷烃产率分别为4.1％和22.8％，有机相中C5-C6烷烃产率分别为30.9％。当水和n-decane的体积比VA/VO＝15/12时，在T＝200℃，p(H2)＝6Mpa，t＝18h作用下，在3％Ru-20％MoOx/C作用下气相中CO和C1-C4烷烃产率分别为2.3％和28.6％(其中LPG获得较高水平的25.2％产率)，有机相中C5-C6烷烃产率分别为46.5％。当水和n-decane的体积比VA/VO＝0/27时，在T＝240℃，p(H2)＝6Mpa，t＝18h作用下，在3％Ru-20％MoOx/C作用下气相中C1-C4烷烃产率分别为56.1％，有机相中C5-C6烷烃产率分别为43.8％。
实施例3：
参考实施例2，采用0.1gα-ZrP，0.2g3％Ru-20％MoOx/C，0.25g纤维素，T＝200℃,p(H2)＝6Mpa,t＝18h，水和n-decane的体积比VA/VO＝15/12进行催化实验时，第一次循环主要产物C5-C6烷烃产率为48.1％，循环3次后，仍可保留38％的产率(见表3)。
表3α-ZrP耦合3％Ru-20％MoOx/C用于催化纤维素制备小分子烃烷
反应条件：0.1gα-ZrP，0.2g3％Ru-20％MoOx/C，0.25g纤维素，T＝200℃,p(H2)＝6Mpa,t＝18h，15mL水，12mLn-decane。
对比例1：
参考实施例2，不同之处在于没有添加3％Ru-20％MoOx/C催化剂，采用0.1gα-ZrP，0.25g纤维素，T＝200℃,p(H2)＝6Mpa,t＝18h，水和n-decane的体积比VA/VO＝15/12时，产物主要为水相中水解产物Glu，其产率为63.8％，催化剂回收循环3次后，仍可保持49％的Glu产率(参见表4)。
表4
反应条件：0.1gα-ZrP，0.25g纤维素，T＝200℃,p(H2)＝6Mpa,t＝18h，15mL水，12mLn-decane
对比例2：
参考实施例2，不同之处在于没有添加磷酸锆(α-ZrP)，采用0.2g3％Ru-20％MoOx/C，0.25g纤维素，T＝200℃,p(H2)＝6Mpa,t＝18h，水和n-decane的体积比VA/VO＝15/12时，有少量的CO(8.7％)C1-C2烷烃(5.4％)，C3-C4烷烃(2.1％)生成，无C5-C6烷烃生成，循环3次后，仍无C5-C6烷烃生成(参见表5)。
表53％Ru-20％MoOx/C用于催化纤维素制备小分子烃烷
反应条件：0.2g3％Ru-20％MoOx/C，0.25g纤维素，T＝200℃,p(H2)＝6Mpa,t＝18h，15mL水，12mLn-decane
通过对比例1和2，说明α-ZrP耦合Ru-MoOx/C对于生产C5-C6烷烃起重要作用。
Claims (1)
1.一种催化纤维素选择性制备小分子烷烃的方法，其特征在于，在水和C10以上的烷烃组成的双相体系中，加入酸性脱水催化剂α-ZrP、Ru-MoOx/C和纤维素，充入氢气，压力为5-7Mpa，反应温度为200-240℃，一步法产C1-C6烷烃和CO燃料；α-ZrP和Ru-MoOx/C的质量比为0.05：0.2-0.15：0.2；Ru-MoOx/C中，Ru和Mo负载量分别为3-5wt.％和10-20wt.％。
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| CN105289601A (zh) * | 2015-12-07 | 2016-02-03 | 中国科学院广州能源研究所 | 一种山梨醇水相加氢制取直链c5/c6烷烃催化剂及其制备方法 |
| CN105597752A (zh) * | 2015-12-22 | 2016-05-25 | 中国科学院广州能源研究所 | 一种糖醇选择性加氢脱氧制取c5，c6烷烃的负载型碳材料催化剂及其制备方法 |
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| CN104888775A (zh) * | 2015-05-19 | 2015-09-09 | 中国科学院广州能源研究所 | 一种用于糖或糖醇水相氢解制c5或c6烷烃的催化剂 |
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