CN106732725B - 氧化镁负载氮掺杂碳基过渡金属催化剂的制备及其应用 - Google Patents
氧化镁负载氮掺杂碳基过渡金属催化剂的制备及其应用 Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
本发明涉及化学领域,特别涉及氧化镁负载氮掺杂碳基过渡金属催化剂的制备及其应用。所述氧化镁负载氮掺杂碳基过渡金属催化剂(M‑C‑N/MgO),M为过渡金属,可以为铜、铁、镍等;金属M的质量分数在5~20%,碳的质量分数在5~15%,氮的质量分数在0.1~2%,氧化镁质量分数在63~90%;氧化镁的比表面积要求大于或等于60m2/g,孔容大于或等于0.1cm3/g。本发明提供的催化剂用于催化醇胺一步合成亚胺,催化活性好,选择性高;催化剂不含贵金属组分,成本低,且合成过程无需再添加氢氧化钾等碱性试剂,也无需使用专用的氧化试剂,环境友好,步骤简单易行。
Description
技术领域
本发明涉及化学领域,特别涉及氧化镁负载氮掺杂碳基过渡金属催化剂的制备及其应用。
背景技术
亚胺是羰基(醛羰基或酮羰基)上的氧原子被氮所取代后形成的一类有机化合物,通式是R2C=NR′,其中R和R′可以是烃基或氢,氮原子还携带一个氢原子或另一些有机物残基。由于亚胺具有亲电性双键,能与其它试剂发生诸如加成、环加成、氧化还原和缩合等反应;并且亚胺可以通过引入不同配位原子(氧、硫、磷)可以得到结构多变的亚胺配体,这些配体与金属离子形成金属配合物,在催化化学、分析化学、生物医学以及材料学等领域均有重要的作用;另外,亚胺类化合物还具有很好的抗菌、抗真菌作用,它的药理学活性和生物学活性使其在医药学和生物无机领域成为引人注目的研究对象。
亚胺类化合物常见的合成方法有一级胺和羰基化合物缩合脱水,腈、胺、羟胺等含氮化合物的还原、硝基化合物与带活泼氢化合物的反应及羰基化合物与金属胺化合物的反应,以及N卤代三苯基胺的Stieglitz重排、烯烃与叠氮酸的Schmidt反应等等,但是这些方法需要昂贵的反应试剂,且步骤复杂、反应条件苛刻,不适合工业应用。目前,胺与醇的缩合一步生成亚胺由于反应体系简单,原料成本低,备受人们关注。然而,此反应体系常见的催化剂多为钌、钯等贵金属络合物,这类均相催化剂存在难以分离,不可回收利用,价格昂贵等缺点。因此,研制一种新型的催化剂来实现亚胺的高效合成迫在眉睫。
发明内容
本发明要解决的技术问题是如何克服现有技术的不足,提供一种氧化镁负载氮掺杂碳基过渡金属催化剂,简写M-C-N/MgO。
所述M-C-N/MgO催化剂中,M为过渡金属,可以为铜、铁、镍等;金属M的质量分数在5~20%,碳的质量分数在5~15%,氮的质量分数在0.1~2%,氧化镁质量分数在63~90%。
所述M-C-N/MgO催化剂中,过渡金属的原料可以为其硝酸盐、乙酸盐;碳源和氮源为乙二胺四乙酸、壳聚糖等;氧化镁的比表面积要求大于或等于60m2/g,孔容大于或等于0.1cm3/g。
本发明所述M-C-N/MgO催化剂制备方法如下:
1)按照上述质量配比称取过渡金属可溶性盐、乙二胺四乙酸或者壳聚糖,加水直至全部溶解得到透明溶液,向此溶液中加入前述质量配比的氧化镁粉末,强力搅拌,并加热50℃~80℃蒸发,直至将水分完全脱除,得到粉末。
2)将上步得到的粉末,置于管式炉内,在氮气气氛中,以2-6℃/min升温至600℃~1000℃,保持0.5~4小时,然后缓慢降至常温,即得M-C-N/MgO。
作为优选,发明还包含上述M-C-N/MgO催化剂在亚胺合成上的应用,本催化剂适用于以芳香醇和芳香胺为原料,甲苯为溶剂,一步合成亚胺。
进一步的,M-C-N/MgO催化剂在亚胺合成方面的具体步骤如下:取芳香醇及芳香醇物质的量的1.2~2.0倍的芳香胺于带冷凝回流装置的反应釜中,加入芳香醇质量5~20%的氧化镁负载氮掺杂碳基过渡金属催化剂,再加入芳香醇质量的4~15倍的甲苯作为溶剂,强力搅拌,加热至60~100℃,反应8~36小时;之后降至室温,向反应混合物加入乙醇直至无固体产物,继续搅拌,然后过滤催化剂,以重复使用;减压蒸馏得到上清液,可得到粗亚胺,用甲苯洗涤粗亚胺,即得纯亚胺产品。
本发明M-C-N/MgO催化剂采用碱性氧化镁为载体,以氮掺杂炭铜为活性组分,炭包覆金属铜,催化活性高,对亚胺选择性好,并且可循环使用,降低了催化剂的使用成本。该催化剂催化醇胺一步合成亚胺,以碱性氧化镁替代添加氢氧化钾等碱性试剂,而且无需使用专用的氧化试剂,只需在空气气氛中反应即可,环境友好,步骤简单。本发明制备的M-C-N/MgO复合型催化剂无贵金属组分,原料廉价,成本低;合成过程易于操作,适合工业化批量生产。
附图说明
图1为实施例1中Cu-C-N/MgO催化剂的扫描电镜图。
图2为实施例1中Cu-C-N/MgO催化剂的XRD谱图。
具体实施方式
下面将结合附图以及具体实施例来详叙本发明的技术特点,但本发明不受其限制。
实施例1
取0.24千克Cu(CH3COO)2·H2O、0.06千克壳聚糖加入水中,搅拌至完全溶解,再向混合溶液中加入0.26千克氧化镁粉末,强力搅拌,在70℃蒸发,直至将水分完全脱除,得到粉末;将上步得到的粉末置于管式炉内,在氮气气氛中,以2℃/min升温至700℃,保持2小时,然后缓慢降至常温,即得Cu-C-N/MgO催化剂。
实施例2
取0.27千克C4H6O4Ni·4H2O、0.06千克壳聚糖加入水中,搅拌至完全溶解,再向混合溶液中加入0.26千克氧化镁粉末,强力搅拌,在70℃蒸发,直至将水分完全脱除,得到粉末;将上步得到的粉末置于管式炉内,在氮气气氛中,以2℃/min升温至700℃,保持2小时,然后缓慢降至常温,即得Ni-C-N/MgO催化剂。
实施例3
取0.24千克Cu(CH3COO)2·H2O、0.06千克壳聚糖加入水中,搅拌至完全溶解,再向混合溶液中加入0.26千克氧化镁粉末,强力搅拌,在70℃蒸发,直至将水分完全脱除,得到粉末;将上步得到的粉末置于管式炉内,在氮气气氛中,以2℃/min升温至900℃,保持2小时,然后缓慢降至常温,即得Cu-C-N/MgO催化剂。
实施例4
取0.36千克Cu(CH3COO)2·H2O、0.06千克壳聚糖加入水中,搅拌至完全溶解,再向混合溶液中加入0.26千克氧化镁粉末,强力搅拌,在70℃蒸发,直至将水分完全脱除,得到粉末;将上步得到的粉末置于管式炉内,在氮气气氛中,以2℃/min升温至700℃,保持2小时,然后缓慢降至常温,即得Cu-C-N/MgO催化剂。
实施例5
取0.24千克Cu(CH3COO)2·H2O、0.1千克壳聚糖加入水中,搅拌至完全溶解,再向混合溶液中加入0.26千克氧化镁粉末,强力搅拌,在70℃蒸发,直至将水分完全脱除,得到粉末;将上步得到的粉末置于管式炉内,在氮气气氛中,以2℃/min升温至700℃,保持2小时,然后缓慢降至常温,即得Cu-C-N/MgO催化剂。
实施例6
取0.24千克Cu(CH3COO)2·H2O、0.06千克乙二胺四乙酸加入水中,搅拌至完全溶解,再向混合溶液中加入0.26千克氧化镁粉末,强力搅拌,在70℃蒸发,直至将水分完全脱除,得到粉末;将上步得到的粉末置于管式炉内,在氮气气氛中,以2℃/min升温至700℃,保持2小时,然后缓慢降至常温,即得Cu-C-N/MgO催化剂。
实施例7
取0.18千克Fe(C2H3OO)2、0.06千克壳聚糖加入水中,搅拌至完全溶解,再向混合溶液中加入0.26千克氧化镁粉末,强力搅拌,在70℃蒸发,直至将水分完全脱除,得到粉末;将上步得到的粉末置于管式炉内,在氮气气氛中,以2℃/min升温至700℃,保持2小时,然后缓慢降至常温,即得Fe-C-N/MgO催化剂。
实施例8
本实施例以苄胺和苯甲醇为原料,说明本发明所述催化剂1-7组实施例的使用。
分别取1.07千克苄胺、1.08千克苯甲醇于装有冷凝回流的反应釜中,接着加入0.52千克的实施例1-7组制备的催化剂,再加入10千克的甲苯作为溶剂,强力搅拌,加热至80℃,反应24小时,降温,向反应混合物加入乙醇,搅拌,过滤分离催化剂,得到清液,用液相色谱检测产率。减压蒸馏清液,得到粗亚胺,再用甲苯洗涤,即得纯亚胺产品。
表1本发明催化剂催化性能
催化剂 | 转化率(%) | 选择性(%) |
实施例1 | 93 | 94 |
实施例2 | 80 | 88 |
实施例3 | 87 | 96 |
实施例4 | 90 | 94 |
实施例5 | 91 | 98 |
实施例6 | 92 | 96 |
实施例7 | 96 | 96 |
上述催化剂的催化性能见表1,由表中数据知,本专利提供的催化剂具有转优异的活性和选择性。
图1为Cu-C-N/MgO催化剂的扫描电镜图。从图中可以看出,Cu-C-N/MgO催化剂为片状,活性组分铜呈颗粒状均匀分散。图2为本催化剂的XRD谱图,衍射图显示主要成分为氧化镁,说明铜分散均匀,而碳为无定型,XRD谱图无法显示。
以上所述,仅是本发明的实施例而已,并非对本发明作任何形式上的限制,任何熟悉本领域的技术人员,在不脱离本发明技术方案范围情况下,利用上述揭示的方法内容对本发明技术方案做出许多可能的变动和修饰,均属于权利要求书保护的范围。
Claims (2)
1.氧化镁负载氮掺杂碳基过渡金属催化剂在亚胺合成方面的应用,其特征在于:催化剂中,过渡金属为铜、铁、镍;过渡金属的质量分数在5~20%,碳的质量分数在5~15%,氮的质量分数在0.1~2%,氧化镁质量分数在63~90%;氧化镁的比表面积大于或等于60m2/g,氧化镁的孔容大于或等于0.1cm3/g;
催化剂的制备步骤如下:
a)按照所述质量配比称取过渡金属可溶性盐、乙二胺四乙酸或者壳聚糖,加水直至全部溶解得到透明溶液,向溶液中加入质量分数在5~15%的氧化镁粉末,强力搅拌,并加热50℃~80℃蒸发,直至水分完全脱除,得到粉末;
b)将步骤(a)得到的粉末,置于管式炉内,在氮气气氛下,以2-6℃/min升温至600℃~1000℃,保持0.5~4小时,然后缓慢降至常温,即得氧化镁负载氮掺杂碳基过渡金属催化剂。
2.根据权利要求1所述的氧化镁负载氮掺杂碳基过渡金属催化剂在亚胺合成方面的应用,其特征在于:以芳香醇和芳香胺为原料,甲苯为溶剂,合成亚胺;
具体步骤:取芳香醇及芳香醇物质的量的1.2~2.0倍的芳香胺于带冷凝回流装置的反应釜中,加入芳香醇质量5~20%的氧化镁负载氮掺杂碳基过渡金属催化剂,再加入芳香醇质量的4~15倍的甲苯作为溶剂;强力搅拌,加热至60~100℃,反应8~36小时;之后降至室温,向反应混合物加入乙醇直至无固体产物,继续搅拌,然后过滤催化剂,以重复使用;减压蒸馏得到上清液,可得到粗亚胺,用苯洗涤粗亚胺,即得纯亚胺产品。
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