CN108395365B - 一种廉价金属配合物催化还原二氧化碳制备甲醇的方法 - Google Patents

一种廉价金属配合物催化还原二氧化碳制备甲醇的方法 Download PDF

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CN108395365B
CN108395365B CN201810316681.0A CN201810316681A CN108395365B CN 108395365 B CN108395365 B CN 108395365B CN 201810316681 A CN201810316681 A CN 201810316681A CN 108395365 B CN108395365 B CN 108395365B
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王万辉
邱立春
王群慧
包明
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Abstract

本发明提供了一种廉价金属配合物催化还原二氧化碳制备甲醇的方法，属于能源与催化技术领域。本发明利用廉价的金属盐分别与含氮单齿配体、NN双齿配体或NNN三齿配体配位，原位生成配合物，在低温常压下催化二氧化碳与硼氢化钠还原生成甲醇。本发明的优点是：采用的金属盐、含氮单齿配体、NN双齿配体或NNN三齿配体廉价易得，成本较低。硼氢化钠在空气中稳定，便于操作。反应条件温和，甲醇产率较高。

Description

一种廉价金属配合物催化还原二氧化碳制备甲醇的方法
技术领域
本发明属于能源与催化技术领域，涉及一种廉价金属配合物催化还原二氧化碳制备甲醇的方法，是一种利用含氮单齿配体、NN双齿配体或者NNN三齿配体与廉价金属盐原位生成配合物，以硼氢化钠为氢源，催化二氧化碳还原生成甲醇的方法。
背景技术
甲醇是一种基础有机原料，广泛用于合成农药、医药、塑料、合成纤维等化学化工领域。同时，甲醇也是一种重要的清洁燃料，甲醇充分燃烧时，只产生二氧化碳和水，不释放二氧化硫、氮氧化物等有毒有害气体；常温下甲醇呈液态，相比甲烷、氢气等其他清洁燃料，甲醇更加便于存储和运输。基于以上优点，甲醇作为一种重要的清洁燃料被广泛用于燃料电池或添加到燃油中。
当前，工业合成甲醇的方法是采用一氧化碳与氢气的合成气，在高温(250～300℃)高压(50～100atm)条件下，利用催化剂催化合成甲醇。相比利用一氧化碳合成甲醇，以二氧化碳为碳源合成甲醇更具有吸引力。廉价且来源广泛的二氧化碳有助于降低工业合成甲醇的生产成本。而二氧化碳是无毒气体，可以减少生产过程中的安全隐患。更为重要的是，以二氧化碳为碳源合成甲醇对于缓解当下的温室效应问题大有裨益。
Figure BDA0001624092290000011
目前，均相催化二氧化碳还原生成甲醇备受关注。均相催化二氧化碳还原合成甲醇多采用氢气、硼烷或者硅烷作为氢源。以氢气为氢源的反应大多在高温高压条件下进行，反应条件苛刻。采用硼烷(HBCat、HBpin、9-BBN、BH3·THF、BH3·SMe2)或者硅烷作为氢源可以降低反应的难度，但是硼烷、硅烷价格昂贵且硼烷在空气中不稳定，不利于反应操作处理。而硼氢化钠是一种相对廉价的盐类，可以在空气中稳定存在。相比于硼烷硅烷，利用硼氢化钠作为氢源，与二氧化碳反应生成甲醇，更具有优势。
发明内容
本发明的目的是提供一种廉价金属配合物催化还原二氧化碳制备甲醇的方法。
本发明的技术方案：
一种廉价金属配合物催化还原二氧化碳制备甲醇的方法，步骤如下：
以含氮化合物作为含氮单齿配体、NN双齿配体或NNN三齿配体，与金属盐原位反应生成金属配合物L1MXn、L2MXn及L3MXn；再以硼氢化钠作为氢源，常压条件下，金属配合物在有机溶剂中催化二氧化碳还原生成甲醇；
具体步骤如下：
在常压二氧化碳的氛围下，将配体与金属盐按照4～1:1的物质的量之比混合，然后加入有机溶剂，配体的浓度为0.001～0.1mol/L，搅拌2～5min，再加入30～600当量的硼氢化钠和有机溶剂，配合物的浓度为0.002～1mol/L；加热使反应体系温度恒定在25～70℃，反应6～24h，然后向反应体系中滴加0.5～2mL 4mol/L的盐酸搅拌0.5～2h使反应终止；
金属配合物L1MXn、L2MXn或L3MXn结构式如下：
配体L1为咪唑或吡唑；
配体L2为N,N,N',N'-四甲基乙二胺、N,N'-二甲基乙二胺、乙二胺、联吡啶、邻菲罗啉、联嘧啶、2-氨甲基吡啶、邻苯二胺、N-(吡啶-2-氨甲基)苯甲酰胺、N-(吡啶-2-氨甲基)对甲基苯磺酰胺；
配体L3为五甲基二乙烯三胺；
M为Fe2+、Co2+、Ni2+、Cu2+、Cu+或Zn2+；
X为F-、Cl-、Br-、I-、SO4 2-或NO3 -；
n＝1，2。
Figure BDA0001624092290000031
M＝Fe2+，Co2+，Ni2+，Cu2+，Zn2+，Cu+
X＝F-，Cl-，Br-，I-，SO4 2-，NO3 -
n＝1，2
所述的有机溶剂为四氢呋喃、二氧六环或乙腈。
所用的配合物为廉价金属盐与含氮配体原位生成的金属配合物，硼氢化钠与原位生成的配合物的物质的量之比为30～600。
所述的配体12的合成方法，步骤如下：
在N2保护下，将苯甲酸和N，N′-羰基二咪唑按照1∶1.2的物质的量之比加入到无水无氧THF中，苯甲酸的浓度为0.01～0.2mol/L，在20～70℃条件下搅拌反应1～5h后停止加热；将2-氨甲基吡啶溶于无水无氧THF中，配成0.01～0.2mol/L的溶液，然后加入到反应体系中，控制反应体系中2-氨甲基吡啶的量与苯甲酸的量相同；室温下搅拌3～12h后停止反应，减压除去THF，加入二氯甲烷后用去离子水进行洗涤3次，有机相用无水Na2SO4干燥，过滤，减压除去溶剂后得粗产品；经柱层析分离，得到淡黄色固体产品，产率为75％。
所述的配体13的合成方法，步骤如下：
在N2保护下，将2-氨甲基吡啶和NaOH按照1:1.2的物质的量之比加入到除氧水中，NaOH的浓度为0.02～2mol/L；将2-氨甲基吡啶溶于无水无氧THF中，配成0.01～0.2mol/L的溶液，然后加入到反应体系中，控制反应体系中2-氨甲基吡啶的量与苯甲酸的量相同；室温下搅拌反应1～12h；停止反应后减压除去THF，残渣加水淋洗过滤，收集滤渣，干燥后得白色固体粗产品；用乙醇和正己烷重结晶，过滤收集晶体，并用正己烷进行淋洗，滤渣真空干燥，得到白色的针状固体产品，产率为78％。
本发明的有益效果：本发明利用廉价易得的含氮单齿配体、NN双齿配体或者NNN三齿配体与廉价金属盐原位生成金属配合物，催化廉价易得的二氧化碳还原合成化工原料和清洁燃料甲醇。反应所用原料在空气中性质稳定，方便操作。该催化反应无需高温高压的条件，在低温常压下即可实现高效转化。配合物的催化效果好，转化率高。同时，反应采用廉价的二氧化碳作为碳源，避免使用价格相对昂贵、且具有毒性的一氧化碳。硼氢化钠作为氢源比硼烷、硅烷等试剂廉价易得，经济适用性更高。
附图说明
图1是配体12的1H NMR谱图。
图2是配体13的1H NMR谱图。
图3是反应后确定样品中甲醇含量的GC检测结果。
图4是反应后确定样品中甲醇含量的1H NMR检测结果。
具体实施方式
以下结合附图和技术方案，进一步说明本发明的具体实施方式。
实施例1
在常压二氧化碳气体氛围下，将0.0036g(0.02mmol)邻菲罗啉、0.0038g(0.02mmol)CuI加入到反应管中，加入四氢呋喃1mL搅拌2min，再加入0.2270g(6mmol)硼氢化钠、9mL四氢呋喃，水浴加热保持反应体系温度恒定保持在25℃，反应12h后，向反应体系中滴加1mL 4mol/L的盐酸搅拌2h使反应停止，甲醇的产率为6％。
实施例2
在常压二氧化碳气体氛围下，将0.0031g(0.02mmol)联嘧啶、0.0038g(0.02mmol)CuI加入到反应管中，加入四氢呋喃1mL搅拌2min，再加入0.2270g(6mmol)硼氢化钠、9mL四氢呋喃，水浴加热保持反应体系温度恒定保持在25℃，反应12h后，向反应体系中滴加1mL4mol/L的盐酸搅拌2h使反应停止，甲醇的产率为35％。
实施例3
在常压二氧化碳气体氛围下，将0.0072g(0.04mmol)咪唑、0.0038g(0.02mmol)CuI加入到反应管中，加入四氢呋喃1mL搅拌2min，再加入0.2270g(6mmol)硼氢化钠、9mL四氢呋喃，水浴加热保持反应体系温度恒定保持在25℃，反应12h后，向反应体系中滴加1mL 4mol/L的盐酸搅拌2h使反应停止，甲醇的产率为16％。
实施例4
在常压二氧化碳气体氛围下，将1mL 0.02mmol/L的N,N,N',N'-四甲基乙二胺的四氢呋喃溶液和0.0038g(0.02mmol)CuI加入到反应管中，搅拌2min。再加入0.2270g(6mmol)硼氢化钠、9mL四氢呋喃，水浴加热保持反应体系温度恒定保持在66℃，反应12h后，向反应体系中滴加1mL 4mol/L的盐酸搅拌2h使反应停止，甲醇的产率为75％。

Claims (3)

1.一种廉价金属配合物催化还原二氧化碳制备甲醇的方法，其特征在于，以含氮化合物作为含氮单齿配体或NN双齿配体，与金属铜盐原位反应生成金属配合物L1CuX或L2CuX；再以硼氢化钠作为氢源，在常压条件下，金属配合物在有机溶剂中催化二氧化碳还原生成甲醇；
具体步骤如下：
在常压二氧化碳的氛围下，将配体与金属铜盐按照4～1:1的物质的量之比混合，然后加入有机溶剂，配体的浓度为0.001～0.1mol/L，搅拌2～5min，再加入30～600当量的硼氢化钠和有机溶剂，配合物的浓度为0.002～1mol/L；加热使反应体系温度恒定在25～70℃，反应6～24h，然后向反应体系中滴加0.5～2mL 4mol/L的盐酸搅拌0.5～2h使反应终止；
金属配合物L1CuX、L2CuX结构式如下：
Figure FDA0002829682820000011
配体L1为咪唑；
配体L2为N,N,N',N'-四甲基乙二胺、N,N'-二甲基乙二胺、乙二胺、邻菲罗啉或联嘧啶；
Cu为+1价；
X为Cl-、Br-或I-。
2.根据权利要求1所述的方法，其特征在于，所述的有机溶剂为四氢呋喃、二氧六环或乙腈。
3.根据权利要求1或2所述的方法，其特征在于，所用的配合物为廉价金属盐与含氮配体原位生成的金属配合物，硼氢化钠与原位生成的配合物的物质的量之比为30～600。
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