CN109529877A - 用NiAgPd/多孔CexCuyOz纳米催化剂催化甲醛脱氢的方法 - Google Patents
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 29
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 14
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 26
- 239000013084 copper-based metal-organic framework Substances 0.000 claims description 20
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 13
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 16
- 239000001257 hydrogen Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
本发明公开了一种用NiAgPd/多孔CexCuyOz纳米催化剂催化甲醛脱氢的方法，属于化学化工技术领域。本发明将制备好的纳米催化剂置于反应器中，将反应器置于水浴中升至一定温度，接着将甲醛和氢氧化钠混合液加入反应器中进行反应，生成的氢气采用排水法收集。与现有的催化剂不同的是：根据本发明，调节催化剂中金属Ni、Ag、Pd的摩尔比及载体前驱体硝酸铈、硝酸铜和2‑甲基咪唑的摩尔比就可以制得用于甲醛脱氢制氢气的高活性、高选择性、高稳定性的纳米催化剂。使用该催化剂进行甲醛脱氢反应，脱氢转化率和选择性均为100％，反应的TOF值大于520h‑1，循环使用4h，反应的TOF值仍大于515h‑1。
Description
技术领域
本发明属于化学化工技术领域，具体涉及用NiAgPd/多孔CexCuyOz纳米催化剂催化甲醛脱氢的方法。
背景技术
甲醛(HCHO)是目前研究较热的一类新型化学氢化物，它具有化学性质温度，常温下为液态，能很好地利用现有的能源装置，被视为最有发展前景的氢燃料电池氢能供应材料之一。其中甲醛分解遵循如下两种路径：路径一，直接分解生成氢气和一氧化碳，脱氢产物一氧化碳极易造成燃料电池催化剂的中毒；路径二，通过水解途径生成氢气和二氧化碳，该过程生成的产物对催化剂无影响，是理想的氢能释放途径。对于两种路径的调控，关键在于开发高效的甲醛脱氢催化剂。
M.Trincado et al.(Nature Communications 2017,8:14990)首次制备了Ru的配合物作为均相催化剂，催化甲醛高效脱氢，该研究开启了以甲醛为储氢载体的高效储氢技术的研究。Chun Wang et al.(Appl.Organometal.Chem.2017,31:3889)报道了Pd/CeO2催化剂的合成及其作为脱氢催化剂在甲醛脱氢过程中的应用。该催化剂的设计开启了非均相甲醛脱氢催化剂的研究。本专利基于载体的优化构建及载体和活性组分的构效关系原理设计该催化剂，旨在提高催化剂的稳定性和活性。
发明内容
本发明的目的是针对现有技术的不足，提供一种用NiAgPd/多孔CexCuyOz纳米催化剂催化甲醛脱氢的方法，以期该NiAgPd/多孔CexCuyOz纳米催化剂在较温和的条件下实现甲醛完全脱氢。
本发明解决其技术问题所采用的技术方案如下。
将制备好的NiAgPd/多孔CexCuyOz纳米催化剂置于反应器中，将反应器置于水浴中升至-5～20℃，接着将摩尔比为1：(0.3～0.9)的甲醛和氢氧化钠混合液加入反应器中进行反应，得到产物氢气；所述的催化剂与混合液质量比为1:(120～160)。
所述的NiAgPd/多孔CexCuyOz纳米催化剂包括Ni、Ag、Pd和多孔CexCuyOz，其中，Ni来源于硝酸镍，Ag来源于硝酸银，Pd来源于氯钯酸钾，多孔CexCuyOz由硝酸铈、硝酸铜与2-甲基咪唑形成Ce-Cu-MOF焙烧制得，硝酸镍与硝酸银、氯钯酸钾的摩尔比为1：(0.2～0.5)：(0.1～0.3)；硝酸镍与硝酸铈、硝酸铜、2-甲基咪唑的摩尔比为1：(2～4)：(5～9)：(21～27)。
所述的NiAgPd/多孔CexCuyOz纳米催化剂是通过以下步骤予以制备的：
(1)将硝酸铈、硝酸铜和2-甲基咪唑溶解于甲醇溶液中形成均一溶液，在24～32℃下搅拌24～29h，离心得到Ce-Cu-MOF；
(2)将Ce-Cu-MOF转移至管式炉，焙烧得到多孔CexCuyOz；
(3)将焙烧得到的多孔CexCuyOz置于硝酸镍、硝酸银和氯钯酸钾溶液，在0～4℃下使用氨硼烷溶液还原3～6h，离心干燥，即制得NiAgPd/多孔CexCuyOz纳米催化剂。
所述的NiAgPd/多孔CexCuyOz纳米催化剂的制备步骤(2)中：管式炉焙烧温度为485～540℃，焙烧时间2～5h，焙烧气氛为O2/N2，其中O2的体积占比为9％～16％。
所述的NiAgPd/多孔CexCuyOz纳米催化剂的制备步骤(3)中：氨硼烷浓度为0.14～0.29mol/L。
与现有技术相比，本发明的有益效果是：
1、本发明采用操作简便、易于工业化应用的浸渍还原法合成催化剂，催化剂载体制备使用价廉易得的硝酸铈、硝酸铜和2-甲基咪唑为前驱体，按一定摩尔比溶解于甲醇溶液中形成均一溶液，在温和的反应条件下反应一定时间，离心得到Ce-Cu-MOF，将Ce-Cu-MOF转移至管式炉，在一定焙烧条件和气氛下焙烧得到多孔CexCuyOz，将焙烧得到的多孔CexCuyOz置于一定组成的硝酸镍、硝酸银和氯钯酸钾溶液，在温和条件下使用氨硼烷溶液还原一段时间，离心干燥，即制得具有高分散性纳米颗粒的NiAgPd/多孔CexCuyOz纳米催化剂。
2、该NiAgPd/多孔CexCuyOz纳米催化剂对甲醛脱氢反应具有较高的活性、选择性和稳定性。使用该催化剂可实现温和条件下甲醛脱氢，脱氢转化率和选择性均为100％，反应的TOF值大于520h-1，循环使用4h，反应的TOF值仍大于515h-1。
具体实施方式
下面通过实施例对本发明做进一步详细说明。但是所述实例不构成对本发明的限制。
实施例1
制备催化剂过程
将2mmol硝酸铈、9mmol硝酸铜和27mmol 2-甲基咪唑溶于溶解于200mL甲醇形成均一溶液，在32℃下搅拌24h，离心得到Ce-Cu-MOF，将Ce-Cu-MOF转移至管式炉，在485℃焙烧时间5h，焙烧气氛为16％O2/N2，焙烧制得多孔CexCuyOz，将制得的多孔CexCuyOz置于含1mmol硝酸镍、0.2mmol硝酸银和0.3mmol氯钯酸钾溶液中，使用0.14mol/L的氨硼烷溶液在0℃还原6h，即制得催化剂，记为NiAg0.2Pd0.3/多孔Ce2Cu9Oz纳米催化剂，密闭保存。
脱氢反应过程
将50mg上述催化剂装至管式反应器中，再将管式反应器置于水浴中控制反应温度为-5℃，向其中滴加摩尔比为1:0.9的甲醛和氢氧化钠混合液6g，收集反应气体，反应后测得氢气的选择性为100％，甲醛的转化率为100％，反应的TOF值为570h-1，循环使用4h，反应的TOF值仍大于564h-1。
实施例2
制备催化剂过程
将4mmol硝酸铈、5mmol硝酸铜和21mmol 2-甲基咪唑溶于溶解于200mL甲醇形成均一溶液，在32℃下搅拌24h，离心得到Ce-Cu-MOF，将Ce-Cu-MOF转移至管式炉，在540℃焙烧时间2h，焙烧气氛为9％O2/N2，焙烧制得多孔CexCuyOz，将制得的多孔CexCuyOz置于含1mmol硝酸镍、0.5mmol硝酸银和0.1mmol氯钯酸钾溶液中，使用0.29mol/L的氨硼烷溶液在4℃还原3h，即制得催化剂，记为NiAg0.5Pd0.1/多孔Ce4Cu5Oz纳米催化剂，密闭保存。
脱氢反应过程
将50mg上述催化剂装至管式反应器中，再将管式反应器置于水浴中控制反应温度为20℃，向其中滴加摩尔比为1:0.3的甲醛和氢氧化钠混合液8g，收集反应气体，反应后测得氢气的选择性为100％，甲醛的转化率为100％，反应的TOF值为680h-1，循环使用4h，反应的TOF值仍大于675h-1。
实施例3
制备催化剂过程
将3mmol硝酸铈、6mmol硝酸铜和23mmol 2-甲基咪唑溶于溶解于200mL甲醇形成均一溶液，在28℃下搅拌24h，离心得到Ce-Cu-MOF，将Ce-Cu-MOF转移至管式炉，在530℃焙烧时间4h，焙烧气氛为11％O2/N2，焙烧制得多孔CexCuyOz，将制得的多孔CexCuyOz置于含1mmol硝酸镍、0.3mmol硝酸银和0.2mmol氯钯酸钾溶液中，使用0.25mol/L的氨硼烷溶液在2℃还原4h，即制得催化剂，记为NiAg0.3Pd0.2/多孔Ce3Cu6Oz纳米催化剂，密闭保存。
脱氢反应过程
将50mg上述催化剂装至管式反应器中，再将管式反应器置于水浴中控制反应温度为5℃，向其中滴加摩尔比为1:0.4的甲醛和氢氧化钠混合液7g，收集反应气体，反应后测得氢气的选择性为100％，甲醛的转化率为100％，反应的TOF值为610h-1，循环使用4h，反应的TOF值仍大于604h-1。
实施例4
制备催化剂过程
将4mmol硝酸铈、6mmol硝酸铜和21mmol 2-甲基咪唑溶于溶解于200mL甲醇形成均一溶液，在28℃下搅拌29h，离心得到Ce-Cu-MOF，将Ce-Cu-MOF转移至管式炉，在490℃焙烧时间4.5h，焙烧气氛为13％O2/N2，焙烧制得多孔CexCuyOz，将制得的多孔CexCuyOz置于含1mmol硝酸镍、0.4mmol硝酸银和0.3mmol氯钯酸钾溶液中，使用0.24mol/L的氨硼烷溶液在2℃还原5h，即制得催化剂，记为NiAg0.4Pd0.3/多孔Ce4Cu6Oz纳米催化剂，密闭保存。
脱氢反应过程
将50mg上述催化剂装至管式反应器中，再将管式反应器置于水浴中控制反应温度为12℃，向其中滴加摩尔比为1:0.8的甲醛和氢氧化钠混合液6.5g，收集反应气体，反应后测得氢气的选择性为100％，甲醛的转化率为100％，反应的TOF值为614h-1，循环使用4h，反应的TOF值仍大于610h-1。
实施例5
制备催化剂过程
将3mmol硝酸铈、8mmol硝酸铜和27mmol 2-甲基咪唑溶于溶解于200mL甲醇形成均一溶液，在26℃下搅拌24h，离心得到Ce-Cu-MOF，将Ce-Cu-MOF转移至管式炉，在530℃焙烧时间4.5h，焙烧气氛为12％O2/N2，焙烧制得多孔CexCuyOz，将制得的多孔CexCuyOz置于含1mmol硝酸镍、0.5mmol硝酸银和0.2mmol氯钯酸钾溶液中，使用0.15mol/L的氨硼烷溶液在1℃还原2.5h，即制得催化剂，记为NiAg0.5Pd0.2/多孔Ce3Cu8Oz纳米催化剂，密闭保存。
脱氢反应过程
将50mg上述催化剂装至管式反应器中，再将管式反应器置于水浴中控制反应温度为20℃，向其中滴加摩尔比为1:0.7的甲醛和氢氧化钠混合液7.3g，收集反应气体，反应后测得氢气的选择性为100％，甲醛的转化率为100％，反应的TOF值为647h-1，循环使用4h，反应的TOF值仍大于641h-1。
实施例6
制备催化剂过程
将3mmol硝酸铈、5mmol硝酸铜和27mmol 2-甲基咪唑溶于溶解于200mL甲醇形成均一溶液，在24℃下搅拌24h，离心得到Ce-Cu-MOF，将Ce-Cu-MOF转移至管式炉，在518℃焙烧时间2.5h，焙烧气氛为16％O2/N2，焙烧制得多孔CexCuyOz，将制得的多孔CexCuyOz置于含1mmol硝酸镍、0.3mmol硝酸银和0.3mmol氯钯酸钾溶液中，使用0.29mol/L的氨硼烷溶液在3℃还原3.5h，即制得催化剂，记为NiAg0.3Pd0.4/多孔Ce3Cu5Oz纳米催化剂，密闭保存。
脱氢反应过程
将50mg上述催化剂装至管式反应器中，再将管式反应器置于水浴中控制反应温度为-5℃，向其中滴加摩尔比为1:0.9的甲醛和氢氧化钠混合液7.8g，收集反应气体，反应后测得氢气的选择性为100％，甲醛的转化率为100％，反应的TOF值为540h-1，循环使用4h，反应的TOF值仍大于534h-1。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施方式仅限于此，对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单的推演和替换，都应当视为属于本发明由所提交的权利要求书确定专利的保护范围。
Claims (3)
1.用NiAgPd/多孔CexCuyOz纳米催化剂催化甲醛脱氢的方法，其特征在于：将制备好的NiAgPd/多孔CexCuyOz纳米催化剂置于反应器中，将反应器置于水浴中升至-5～20℃，接着将摩尔比为1：(0.3～0.9)的甲醛和氢氧化钠混合液加入反应器中进行反应，得到产物氢气；
所述的催化剂与混合液质量比为1:(120～160)；
所述的NiAgPd/多孔CexCuyOz纳米催化剂包括Ni、Ag、Pd和多孔CexCuyOz，其中，Ni来源于硝酸镍，Ag来源于硝酸银，Pd来源于氯钯酸钾，多孔CexCuyOz由硝酸铈、硝酸铜与2-甲基咪唑形成Ce-Cu-MOF焙烧制得，硝酸镍与硝酸银、氯钯酸钾的摩尔比为1：(0.2～0.5)：(0.1～0.3)；硝酸镍与硝酸铈、硝酸铜、2-甲基咪唑的摩尔比为1：(2～4)：(5～9)：(21～27)；
所述的NiAgPd/多孔CexCuyOz纳米催化剂是通过以下步骤予以制备的：
(1)将硝酸铈、硝酸铜和2-甲基咪唑溶解于甲醇溶液中形成均一溶液，在24～32℃下搅拌24～29h，离心得到Ce-Cu-MOF；
(2)将Ce-Cu-MOF转移至管式炉，焙烧得到多孔CexCuyOz；
(3)将焙烧得到的多孔CexCuyOz置于硝酸镍、硝酸银和氯钯酸钾溶液，在0～4℃下使用氨硼烷溶液还原3～6h，离心干燥，即制得NiAgPd/多孔CexCuyOz纳米催化剂。
2.如权利要求1所述的用NiAgPd/多孔CexCuyOz纳米催化剂催化甲醛脱氢的方法，其特征在于，所述的NiAgPd/多孔CexCuyOz纳米催化剂的制备步骤(2)中：管式炉焙烧温度为485～540℃，焙烧时间2～5h，焙烧气氛为O2/N2，其中O2的体积占比为9％～16％。
3.如权利要求1所述的用NiAgPd/多孔CexCuyOz纳米催化剂催化甲醛脱氢的方法，其特征在于，所述的NiAgPd/多孔CexCuyOz纳米催化剂的制备步骤(3)中：氨硼烷浓度为0.14～0.29mol/L。
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