Martín N. Gatti, Federico M. Perez, Gerardo F. Santori, Francisco Pompeo
{"title":"甘油氢解制生物丙醇:Al(H2PO4)3改性Ni/C的催化活性及动力学模型","authors":"Martín N. Gatti, Federico M. Perez, Gerardo F. Santori, Francisco Pompeo","doi":"10.3390/reactions4040039","DOIUrl":null,"url":null,"abstract":"The aim of the present research is to investigate the effect of different operation variables in the hydrogenolysis of glycerol to 1-propanol and to develop a simple kinetic model useful for the design of the reactor. For this purpose, a carbon-based composite was impregnated with 4 wt.% of Al(H2PO4)3 (CPAl) and used as a support to prepare a Ni catalyst. The support and the catalyst were characterized by BET, XRD, NMR, potentiometric titration, isopropanol decomposition reaction, TEM and TPR analysis. The catalytic tests were carried out at 220–260 °C and 0.5–4 MPa of H2 initial pressure varying the glycerol concentration in aqueous solutions between 30 and 80 wt.%. The presence of aluminum phosphates in the Ni/CPAl catalyst moderates the surface acidity and the formation of Ni2P leads to a high selectivity towards 1-propanol. In this sense, the Ni/CPAl catalyst showed total glycerol conversion and 74% selectivity towards 1-propanol at 260 °C and 2 MPa of H2 initial pressure using 30 wt.% glycerol aqueous solution and 8 h of reaction time. A slight increase in particle size from 10 to 12 nm was observed after a first reaction cycle, but no changes in acidity and structure were observed. Based on these results, a power-law kinetic model was proposed. For glycerol consumption, partial orders of 0.07, 0.68 and −0.98 were determined with respect to glycerol, H2 and water, and an apparent activation energy of 89 kJ mol−1 was estimated. The results obtained indicate that the model fits the experimental concentration values well and can predict them with an average error of less than 7%.","PeriodicalId":20873,"journal":{"name":"Reactions","volume":"35 4","pages":"0"},"PeriodicalIF":0.0000,"publicationDate":"2023-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Glycerol Hydrogenolysis to Bio-Propanol: Catalytic Activity and Kinetic Model for Ni/C Modified with Al(H2PO4)3\",\"authors\":\"Martín N. Gatti, Federico M. Perez, Gerardo F. Santori, Francisco Pompeo\",\"doi\":\"10.3390/reactions4040039\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The aim of the present research is to investigate the effect of different operation variables in the hydrogenolysis of glycerol to 1-propanol and to develop a simple kinetic model useful for the design of the reactor. For this purpose, a carbon-based composite was impregnated with 4 wt.% of Al(H2PO4)3 (CPAl) and used as a support to prepare a Ni catalyst. The support and the catalyst were characterized by BET, XRD, NMR, potentiometric titration, isopropanol decomposition reaction, TEM and TPR analysis. The catalytic tests were carried out at 220–260 °C and 0.5–4 MPa of H2 initial pressure varying the glycerol concentration in aqueous solutions between 30 and 80 wt.%. The presence of aluminum phosphates in the Ni/CPAl catalyst moderates the surface acidity and the formation of Ni2P leads to a high selectivity towards 1-propanol. In this sense, the Ni/CPAl catalyst showed total glycerol conversion and 74% selectivity towards 1-propanol at 260 °C and 2 MPa of H2 initial pressure using 30 wt.% glycerol aqueous solution and 8 h of reaction time. A slight increase in particle size from 10 to 12 nm was observed after a first reaction cycle, but no changes in acidity and structure were observed. Based on these results, a power-law kinetic model was proposed. For glycerol consumption, partial orders of 0.07, 0.68 and −0.98 were determined with respect to glycerol, H2 and water, and an apparent activation energy of 89 kJ mol−1 was estimated. The results obtained indicate that the model fits the experimental concentration values well and can predict them with an average error of less than 7%.\",\"PeriodicalId\":20873,\"journal\":{\"name\":\"Reactions\",\"volume\":\"35 4\",\"pages\":\"0\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2023-11-05\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Reactions\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.3390/reactions4040039\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Reactions","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.3390/reactions4040039","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Glycerol Hydrogenolysis to Bio-Propanol: Catalytic Activity and Kinetic Model for Ni/C Modified with Al(H2PO4)3
The aim of the present research is to investigate the effect of different operation variables in the hydrogenolysis of glycerol to 1-propanol and to develop a simple kinetic model useful for the design of the reactor. For this purpose, a carbon-based composite was impregnated with 4 wt.% of Al(H2PO4)3 (CPAl) and used as a support to prepare a Ni catalyst. The support and the catalyst were characterized by BET, XRD, NMR, potentiometric titration, isopropanol decomposition reaction, TEM and TPR analysis. The catalytic tests were carried out at 220–260 °C and 0.5–4 MPa of H2 initial pressure varying the glycerol concentration in aqueous solutions between 30 and 80 wt.%. The presence of aluminum phosphates in the Ni/CPAl catalyst moderates the surface acidity and the formation of Ni2P leads to a high selectivity towards 1-propanol. In this sense, the Ni/CPAl catalyst showed total glycerol conversion and 74% selectivity towards 1-propanol at 260 °C and 2 MPa of H2 initial pressure using 30 wt.% glycerol aqueous solution and 8 h of reaction time. A slight increase in particle size from 10 to 12 nm was observed after a first reaction cycle, but no changes in acidity and structure were observed. Based on these results, a power-law kinetic model was proposed. For glycerol consumption, partial orders of 0.07, 0.68 and −0.98 were determined with respect to glycerol, H2 and water, and an apparent activation energy of 89 kJ mol−1 was estimated. The results obtained indicate that the model fits the experimental concentration values well and can predict them with an average error of less than 7%.