CN111468129B - 一种用于甲醛乙炔化反应的纳米片催化剂的制备方法 - Google Patents
一种用于甲醛乙炔化反应的纳米片催化剂的制备方法 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims abstract description 28
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 28
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
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- 238000001914 filtration Methods 0.000 claims description 14
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- 239000011777 magnesium Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- KVLCHQHEQROXGN-UHFFFAOYSA-N aluminium(1+) Chemical compound [Al+] KVLCHQHEQROXGN-UHFFFAOYSA-N 0.000 claims description 2
- 229940007076 aluminum cation Drugs 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000002336 sorption--desorption measurement Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 7
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 6
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 6
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
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- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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Abstract
一种用于甲醛乙炔化反应的纳米片催化剂的制备方法，属于催化剂制备技术领域，可解决高活性甲醛乙炔化反应过程中反应物与催化活性组分的有效接触面积有限的问题，采用如下方案：将含铜类水滑石置于铜盐前驱体水溶液中进行浸渍；将浸渍后的含铜类水滑石在超临界乙醇中剥离成纳米片，即得本发明所述用于甲醛乙炔化反应的纳米片催化剂。在甲醛乙炔化反应制备1,4‑丁炔二醇的反应中，该催化剂的甲醛转化率>70%，对1,4‑丁炔二醇的选择性>80%。该催化剂实现了铜催化活性物种在纳米片上的高度分散，并基于纳米片的二维平面结构，减少了反应物及产物在常规催化剂孔道中的吸附‑脱附过程。
Description
技术领域
本发明属于催化剂制备技术领域，具体涉及一种用于甲醛乙炔化反应的纳米片催化剂的制备方法。
背景技术
1,4-丁炔二醇是一种重要的有机化工原料。以1,4-丁炔二醇为源头，可以延伸出1,4-丁二醇、四氢呋喃、γ-丁内酯等高附加值产业链。目前，1,4-丁炔二醇主要以甲醛和乙炔为原料，采用铜铋催化剂，基于淤浆床工艺进行生产。由于该反应是在乙炔气体、液态甲醛、固体催化剂的多相体系内进行，如何提高反应物与催化活性组分的有效接触，已成为高活性甲醛乙炔化催化剂研发中必须解决的关键问题之一。
纳米片是一类水平尺寸超过100纳米，但厚度不超过几个纳米的片状二维材料。由于纳米片不存在孔道结构，因而可以最大程度地减少反应物、产物在催化剂孔道中的吸附、脱附过程，有利于提高反应速率。类水滑石是一类具有层状结构的无机化合物，将其层板进行剥离可制备纳米片。
发明内容
本发明针对高活性甲醛乙炔化反应过程中反应物与催化活性组分的有效接触面积有限的问题，提供一种用于甲醛乙炔化反应的纳米片催化剂的制备方法。
本发明采用如下技术方案：
一种用于甲醛乙炔化反应的纳米片催化剂的制备方法，包括如下步骤：
第一步，将含铜类水滑石置于铜盐水溶液中，进行浸渍1-24h，得到混合物；
第二步，将第一步得到的混合物过滤，得到浸渍后的含铜类水滑石；
第三步，将浸渍后的含铜类水滑石分散于无水乙醇中，得到混合液，其中，含铜类水滑石在无水乙醇中的浓度为0.1-1g/L；
第四步，将第三步得到的混合液加入到超临界反应釜中，调节温度240-300℃之间，保持混合液处于乙醇的超临界状态下15-120min；
第五步，反应结束后，恢复到常温常压后，过滤，收集固体，干燥后得到用于甲醛乙炔化反应的纳米片催化剂。
第一步中所述含铜类水滑石的组成通式为CuxM3-xAl-LDHs，其中M包括二价镁和锌金属阳离子中的任意一种，Al为三价铝阳离子，x为0.1-2。
第一步中所述铜盐包括硝酸铜和醋酸铜中的任意一种。
第一步中所述铜盐水溶液的浓度为0.01-0.1g/L，含铜类水滑石在铜盐水溶液中浓度为0.1-1g/L。
本发明将含铜类水滑石浸渍于铜盐水溶液中，后通过超临界乙醇将其剥离为纳米片。在超临界剥离过程中，浸渍的铜盐将聚集在类水滑石层板二价阳离子铜的周围，并被还原为氧化亚铜，最终形成了以含铜类水滑石纳米片为载体，以高度分散氧化亚铜为催化活性物质的甲醛乙炔化催化剂。
本发明的有益效果如下：
1. 本发明基于纳米片的二维平面结构，其厚度仅为几个纳米，不存在常规催化剂的孔道结构，甲醛乙炔化反应仅在纳米片表面进行，避免了反应物和产物在常规催化剂孔道中的“扩散-吸附-脱附”过程，有效提高了反应速率。
2. 本发明通过浸渍法将铜盐负载到类水滑石上，在利用超临界乙醇剥离类水滑石制备纳米片的同时，将二价铜盐还原为氧化亚铜活性物种，实现了纳米片制备、氧化亚铜活性物种制备两个步骤一次进行，简化了制备流程。
3、本发明利用类水滑石层板中的二价铜离子的高分散性，将还原的氧化亚铜聚集在层板二价铜物种周围，实现了氧化亚铜在类水滑石纳米片上的高分散，提高了催化活性。
具体实施方式
实施例1
将0.1g的组成通式为Cu0.1Mg2.9Al-LDHs的含铜类水滑石加入到100mL浓度为0.05g/L的硝酸铜水溶液中，缓慢搅拌24小时；过滤后得到浸渍后含铜类水滑石；将浸渍后含铜类水滑石分散到100mL无水乙醇中；将上述混合液加入到超临界反应釜中，升温到240℃，保持60分钟；恢复到常温、常压后，过滤收集固体，干燥后得到纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至90℃，搅拌条件下通入乙炔气，反应24h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率70.5%，对1,4-丁炔二醇的选择性82.5%。
实施例2
将0.1g的组成通式为Cu1.0Mg2.0Al-LDHs的含铜类水滑石加入到200mL浓度为0.05g/L的醋酸铜水溶液中，缓慢搅拌12小时；过滤后得到浸渍后含铜类水滑石；将浸渍后含铜类水滑石分散到200mL无水乙醇中；将上述混合液加入到超临界反应釜中，升温到300℃，保持15分钟；恢复到常温、常压后，过滤收集固体，干燥后得到纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至90℃，搅拌条件下通入乙炔气，反应24h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率73%，对1,4-丁炔二醇的选择性81.1%。
实施例3
将0.1g的组成通式为Cu1.0Mg2.0Al-LDHs的含铜类水滑石加入到200mL浓度为0.05g/L的醋酸铜水溶液中，缓慢搅拌12小时；过滤后得到浸渍后含铜类水滑石；将浸渍后含铜类水滑石分散到200mL无水乙醇中；将上述混合液加入到超临界反应釜中，升温到300℃，保持15分钟；恢复到常温、常压后，过滤收集固体，干燥后得到纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至90℃，搅拌条件下通入乙炔气，反应24h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率73%，对1,4-丁炔二醇的选择性81.1%。
实施例4
将0.1g的组成通式为Cu2.0Mg1.0Al-LDHs的含铜类水滑石加入到500mL浓度为0.01g/L的硝酸铜水溶液中，缓慢搅拌12小时；过滤后得到浸渍后含铜类水滑石；将浸渍后含铜类水滑石分散到500mL无水乙醇中；将上述混合液加入到超临界反应釜中，升温到280℃，保持30分钟；恢复到常温、常压后，过滤收集固体，干燥后得到纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至90℃，搅拌条件下通入乙炔气，反应24h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率73.6%，对1,4-丁炔二醇的选择性81.8%。
实施例5
将0.1g的组成通式为Cu1.5Mg1.5Al-LDHs的含铜类水滑石加入到500mL浓度为0.05g/L的醋酸铜水溶液中，缓慢搅拌1小时；过滤后得到浸渍后含铜类水滑石；将浸渍后含铜类水滑石分散到500mL无水乙醇中；将上述混合液加入到超临界反应釜中，升温到280℃，保持40分钟；恢复到常温、常压后，过滤收集固体，干燥后得到纳米片催化剂。
将0.1g纳米片催化剂与10 mL甲醛(35%)水溶液装入圆底烧瓶中，通氮气吹扫0.5h，加热至90℃，搅拌条件下通入乙炔气，反应24h。反应后的物料采用气相色谱仪进行组份分析，未反应的甲醛采用碘量法测定。该纳米片催化剂对甲醛转化率74.3%，对1,4-丁炔二醇的选择性85.1%。
Claims (3)
1.一种用于甲醛乙炔化反应的纳米片催化剂的制备方法，其特征在于：包括如下步骤：
第一步，将含铜类水滑石置于铜盐水溶液中，进行浸渍1-24h，得到混合物；
第二步，将第一步得到的混合物过滤，得到浸渍后的含铜类水滑石；
第三步，将浸渍后的含铜类水滑石分散于无水乙醇中，得到混合液，其中，含铜类水滑石在无水乙醇中的浓度为0.1-1g/L；
第四步，将第三步得到的混合液加入到超临界反应釜中，调节温度240-300℃之间，保持混合液处于乙醇的超临界状态下15-120min；
第五步，反应结束后，恢复到常温常压后，过滤，收集固体，干燥后得到用于甲醛乙炔化反应的纳米片催化剂；
第一步中所述含铜类水滑石的组成通式为CuxM3-xAl-LDHs，其中M包括二价镁和锌金属阳离子中的任意一种，Al为三价铝阳离子，x为0.1-2。
2.根据权利要求1所述的一种用于甲醛乙炔化反应的纳米片催化剂的制备方法，其特征在于：第一步中所述铜盐包括硝酸铜和醋酸铜中的任意一种。
3.根据权利要求1所述的一种用于甲醛乙炔化反应的纳米片催化剂的制备方法，其特征在于：第一步中所述铜盐水溶液的浓度为0.01-0.1g/L，含铜类水滑石在铜盐水溶液中浓度为0.1-1g/L。
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