{"title":"用喹啉/十氢喹啉对作为 LOHC 底物,镁修饰的高负载镍催化剂在储氢/萃取中的效率","authors":"","doi":"10.1016/j.jma.2024.07.014","DOIUrl":null,"url":null,"abstract":"<div><div>An effect of Mg introduction on efficiency of high-loaded nickel catalysts in dehydrogenation of decahydroquinoline (10HQ) was investigated. 10HQ dehydrogenation is key process for the liquid organic hydrogen carrier (LOHC) storage technology using the quinoline/10HQ pair as H<sub>2</sub>-lean/H<sub>2</sub>-rich substrates. An influence of synthesis technique of Ni/Mg/Al catalysts on their properties has been demonstrated. The catalysts were synthesized through coprecipitation of Ni, Mg, Al precursors to obtain layered double hydroxides (LDH) or via synthesis of (∼72 wt%) Ni-Al<sub>2</sub>O<sub>3</sub> system – also through coprecipitation, followed by modifying with a magnesium-containing precursor. For the catalysts of the first series, the inclusion of magnesium into LDH lattice led to a significant increase in catalytic activity in hydrogen extraction (10HQ dehydrogenation reaction). Despite the decrease in the content of catalytically active nickel, a significant increase in the yield of the dehydrogenation product was observed. This regularity is presumably associated with appearance of basic sites, that accelerates the dehydrogenation reaction. In the case of the second series, activity of pre-reduced (600 °C, H<sub>2</sub>) catalysts in dehydrogenation of 10HQ also significantly depends on a MgO content and is maximal at Mg:Ni weight ratio 0.056. Using an in-depth study of structure of the original and reduced catalyst samples (Ni-Al<sub>2</sub>O<sub>3</sub> and Ni-MgNiO<sub><em>x</em></sub>-Al<sub>2</sub>O<sub>3</sub>), it was shown that this regularity is associated with the increased resistance of catalytically active Ni particles to agglomeration during the reductive activation. Also, using the Ni-MgNiO<sub>x</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst for hydrogen storage process (hydrogenation reaction), the possibility of deep quinoline hydrogenation (up to 10HQ) in a flow-type reactor was demonstrated for the first time.</div></div>","PeriodicalId":16214,"journal":{"name":"Journal of Magnesium and Alloys","volume":null,"pages":null},"PeriodicalIF":15.8000,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2213956724002585/pdfft?md5=8178721061fbf3231abbd64f08c13df7&pid=1-s2.0-S2213956724002585-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Efficiency of high-loaded nickel catalysts modified by Mg in hydrogen storage/extraction using quinoline/decahydroquinoline pair as LOHC substrates\",\"authors\":\"\",\"doi\":\"10.1016/j.jma.2024.07.014\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>An effect of Mg introduction on efficiency of high-loaded nickel catalysts in dehydrogenation of decahydroquinoline (10HQ) was investigated. 10HQ dehydrogenation is key process for the liquid organic hydrogen carrier (LOHC) storage technology using the quinoline/10HQ pair as H<sub>2</sub>-lean/H<sub>2</sub>-rich substrates. An influence of synthesis technique of Ni/Mg/Al catalysts on their properties has been demonstrated. The catalysts were synthesized through coprecipitation of Ni, Mg, Al precursors to obtain layered double hydroxides (LDH) or via synthesis of (∼72 wt%) Ni-Al<sub>2</sub>O<sub>3</sub> system – also through coprecipitation, followed by modifying with a magnesium-containing precursor. For the catalysts of the first series, the inclusion of magnesium into LDH lattice led to a significant increase in catalytic activity in hydrogen extraction (10HQ dehydrogenation reaction). Despite the decrease in the content of catalytically active nickel, a significant increase in the yield of the dehydrogenation product was observed. This regularity is presumably associated with appearance of basic sites, that accelerates the dehydrogenation reaction. In the case of the second series, activity of pre-reduced (600 °C, H<sub>2</sub>) catalysts in dehydrogenation of 10HQ also significantly depends on a MgO content and is maximal at Mg:Ni weight ratio 0.056. Using an in-depth study of structure of the original and reduced catalyst samples (Ni-Al<sub>2</sub>O<sub>3</sub> and Ni-MgNiO<sub><em>x</em></sub>-Al<sub>2</sub>O<sub>3</sub>), it was shown that this regularity is associated with the increased resistance of catalytically active Ni particles to agglomeration during the reductive activation. Also, using the Ni-MgNiO<sub>x</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst for hydrogen storage process (hydrogenation reaction), the possibility of deep quinoline hydrogenation (up to 10HQ) in a flow-type reactor was demonstrated for the first time.</div></div>\",\"PeriodicalId\":16214,\"journal\":{\"name\":\"Journal of Magnesium and Alloys\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":15.8000,\"publicationDate\":\"2024-08-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S2213956724002585/pdfft?md5=8178721061fbf3231abbd64f08c13df7&pid=1-s2.0-S2213956724002585-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Magnesium and Alloys\",\"FirstCategoryId\":\"88\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2213956724002585\",\"RegionNum\":1,\"RegionCategory\":\"材料科学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"METALLURGY & METALLURGICAL ENGINEERING\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Magnesium and Alloys","FirstCategoryId":"88","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2213956724002585","RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"METALLURGY & METALLURGICAL ENGINEERING","Score":null,"Total":0}
Efficiency of high-loaded nickel catalysts modified by Mg in hydrogen storage/extraction using quinoline/decahydroquinoline pair as LOHC substrates
An effect of Mg introduction on efficiency of high-loaded nickel catalysts in dehydrogenation of decahydroquinoline (10HQ) was investigated. 10HQ dehydrogenation is key process for the liquid organic hydrogen carrier (LOHC) storage technology using the quinoline/10HQ pair as H2-lean/H2-rich substrates. An influence of synthesis technique of Ni/Mg/Al catalysts on their properties has been demonstrated. The catalysts were synthesized through coprecipitation of Ni, Mg, Al precursors to obtain layered double hydroxides (LDH) or via synthesis of (∼72 wt%) Ni-Al2O3 system – also through coprecipitation, followed by modifying with a magnesium-containing precursor. For the catalysts of the first series, the inclusion of magnesium into LDH lattice led to a significant increase in catalytic activity in hydrogen extraction (10HQ dehydrogenation reaction). Despite the decrease in the content of catalytically active nickel, a significant increase in the yield of the dehydrogenation product was observed. This regularity is presumably associated with appearance of basic sites, that accelerates the dehydrogenation reaction. In the case of the second series, activity of pre-reduced (600 °C, H2) catalysts in dehydrogenation of 10HQ also significantly depends on a MgO content and is maximal at Mg:Ni weight ratio 0.056. Using an in-depth study of structure of the original and reduced catalyst samples (Ni-Al2O3 and Ni-MgNiOx-Al2O3), it was shown that this regularity is associated with the increased resistance of catalytically active Ni particles to agglomeration during the reductive activation. Also, using the Ni-MgNiOx-Al2O3 catalyst for hydrogen storage process (hydrogenation reaction), the possibility of deep quinoline hydrogenation (up to 10HQ) in a flow-type reactor was demonstrated for the first time.
期刊介绍:
The Journal of Magnesium and Alloys serves as a global platform for both theoretical and experimental studies in magnesium science and engineering. It welcomes submissions investigating various scientific and engineering factors impacting the metallurgy, processing, microstructure, properties, and applications of magnesium and alloys. The journal covers all aspects of magnesium and alloy research, including raw materials, alloy casting, extrusion and deformation, corrosion and surface treatment, joining and machining, simulation and modeling, microstructure evolution and mechanical properties, new alloy development, magnesium-based composites, bio-materials and energy materials, applications, and recycling.