Pub Date : 2024-10-01DOI: 10.1016/S1872-5813(24)60451-2
TANG Bowen, ZHANG Rui, LIU Haiyun, JIN Lijun, HU Haoquan
Direct coal liquefaction (DCL) under CO or syngas atmosphere is beneficial to reduce the cost of hydrogen production. Effects of CO on liquefaction process of Shangwan coal were investigated by comparing the liquefaction behavior in three atmospheres of CO, H2, and N2. Then, effects of different CO/H2 ratios and catalysts on the liquefaction process in syngas were investigated. The results indicated that the oil yield under CO atmosphere reached 43.1%, which was 4.2% lower than that under H2, but 10.2% higher than that under N2. The liquefaction performance was further improved by adding the Shenhua 863 catalyst. It is analyzed that CO promoted liquefaction in two ways: water-gas shift reaction and the reaction between CO and organic structures of coal. Through characterization of the products by GC-MS and FT-IR, it was found that CO makes benzenes, aliphatics, and oxygen-containing compounds in liquefied oil simultaneously increased. The effect on functional groups and free radicals concentration in the solid products was not obvious. The experimental results under syngas showed that the highest oil yield, 57.4%, can be obtained in DCL with 20% CO syngas, and further improved by increasing moisture content of coal appropriately. In addition, the Shenhua 863 catalyst had a good catalytic effect on the liquefaction process and also water-gas shift reaction.
在 CO 或合成气气氛下进行煤直接液化（DCL）有利于降低制氢成本。通过比较 CO、H2 和 N2 三种气氛下的液化行为，研究了 CO 对上湾煤液化过程的影响。然后，研究了不同 CO/H2 比率和催化剂对合成气液化过程的影响。结果表明，CO气氛下的产油率达到43.1%，比H2气氛下低4.2%，但比N2气氛下高10.2%。加入神华 863 催化剂后，液化性能进一步提高。据分析，CO 促进液化的方式有两种：水煤气变换反应和 CO 与煤的有机结构反应。通过 GC-MS 和 FT-IR 对产物的表征发现，CO 使液化油中的苯类、脂肪族和含氧化合物同时增加。对固体产物中官能团和自由基浓度的影响并不明显。合成气条件下的实验结果表明，在使用 20% CO 合成气的 DCL 中，可获得最高的出油率（57.4%），并可通过适当提高煤的含水率进一步提高出油率。此外，神华 863 催化剂对液化过程和水煤气变换反应均有良好的催化效果。
{"title":"Direct liquefaction behavior of Shenhua Shangwan coal under CO containing atmosphere","authors":"TANG Bowen, ZHANG Rui, LIU Haiyun, JIN Lijun, HU Haoquan","doi":"10.1016/S1872-5813(24)60451-2","DOIUrl":"10.1016/S1872-5813(24)60451-2","url":null,"abstract":"<div><div>Direct coal liquefaction (DCL) under CO or syngas atmosphere is beneficial to reduce the cost of hydrogen production. Effects of CO on liquefaction process of Shangwan coal were investigated by comparing the liquefaction behavior in three atmospheres of CO, H<sub>2,</sub> and N<sub>2</sub>. Then, effects of different CO/H<sub>2</sub> ratios and catalysts on the liquefaction process in syngas were investigated. The results indicated that the oil yield under CO atmosphere reached 43.1%, which was 4.2% lower than that under H<sub>2</sub>, but 10.2% higher than that under N<sub>2</sub>. The liquefaction performance was further improved by adding the Shenhua 863 catalyst. It is analyzed that CO promoted liquefaction in two ways: water-gas shift reaction and the reaction between CO and organic structures of coal. Through characterization of the products by GC-MS and FT-IR, it was found that CO makes benzenes, aliphatics, and oxygen-containing compounds in liquefied oil simultaneously increased. The effect on functional groups and free radicals concentration in the solid products was not obvious. The experimental results under syngas showed that the highest oil yield, 57.4%, can be obtained in DCL with 20% CO syngas, and further improved by increasing moisture content of coal appropriately. In addition, the Shenhua 863 catalyst had a good catalytic effect on the liquefaction process and also water-gas shift reaction.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 10","pages":"Pages 1375-1386"},"PeriodicalIF":0.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1016/S1872-5813(24)60460-3
WANG Yuning , GONG Jiesong , ZHOU Jiabin , CHEN Zhiyuan , TIAN Dong , NA Wei , GAO Wengui
In this study, the hydrogenation of carbon dioxide (CO2) to methanol (CH3OH) over Rh16/In2O3 catalyst was studied through Density Functional Theory (DFT) and microdynamics modeling. The spontaneous dissociation mechanisms of H2 and CO2 adsorption at the Rh16/In2O3 interface were investigated. The oxygen vacancies in In2O3 enhanced the adsorption process. Bader charge analysis revealed a marginal positive charge on Rh16, elucidating the critical insights into the electronic characteristics and catalytic activity. The study established the RWGS+CO-Hydro pathway as the predominant mechanism for methanol synthesis, characterized by a sequential transformation of intermediates: CO2*→COOH*→CO*+OH*→HCO*→CH2O*→CH2OH*→CH3OH*. Furthermore, Degree of Reaction Rate Control (DRC) analysis conducted in the range of 373–873 K and 10–2 to 103 bar identified two principal kinetic phenomena: at lower temperature and higher pressure, the conversion of CO* + H* to HCO* significantly impacted the overall reaction rate. Conversely, at higher temperature, the step from CH2O* + H* to CH3O* was dominate.
{"title":"Mechanism of methanol synthesis from CO2 hydrogenation over Rh16/In2O3 catalysts: A combined study on density functional theory and microkinetic modeling","authors":"WANG Yuning , GONG Jiesong , ZHOU Jiabin , CHEN Zhiyuan , TIAN Dong , NA Wei , GAO Wengui","doi":"10.1016/S1872-5813(24)60460-3","DOIUrl":"10.1016/S1872-5813(24)60460-3","url":null,"abstract":"<div><div>In this study, the hydrogenation of carbon dioxide (CO<sub>2</sub>) to methanol (CH<sub>3</sub>OH) over Rh<sub>16</sub>/In<sub>2</sub>O<sub>3</sub> catalyst was studied through Density Functional Theory (DFT) and microdynamics modeling. The spontaneous dissociation mechanisms of H<sub>2</sub> and CO<sub>2</sub> adsorption at the Rh<sub>16</sub>/In<sub>2</sub>O<sub>3</sub> interface were investigated. The oxygen vacancies in In<sub>2</sub>O<sub>3</sub> enhanced the adsorption process. Bader charge analysis revealed a marginal positive charge on Rh<sub>16</sub>, elucidating the critical insights into the electronic characteristics and catalytic activity. The study established the RWGS+CO-Hydro pathway as the predominant mechanism for methanol synthesis, characterized by a sequential transformation of intermediates: CO<sub>2</sub>*→COOH*→CO*+OH*→HCO*→CH<sub>2</sub>O*→CH<sub>2</sub>OH*→CH<sub>3</sub>OH*. Furthermore, Degree of Reaction Rate Control (DRC) analysis conducted in the range of 373–873 K and 10<sup>–2</sup> to 10<sup>3</sup> bar identified two principal kinetic phenomena: at lower temperature and higher pressure, the conversion of CO* + H* to HCO* significantly impacted the overall reaction rate. Conversely, at higher temperature, the step from CH<sub>2</sub>O* + H* to CH<sub>3</sub>O* was dominate.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 10","pages":"Pages 1462-1473"},"PeriodicalIF":0.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1016/S1872-5813(24)60459-7
HUANG Min , BO Qifei , LI Juan , QIAO Jingxuan , YUAN Shanliang , ZHANG Biao , CHEN Honglin , JIANG Yi
A series of Cu/ZnO/Al2O3 catalysts were prepared by co-precipitation method. This research focuses on investigating the influence of different Al2O3 precursors on the catalyst structure through thorough structural characterization techniques. Additionally, the catalytic performance of these catalysts in methanol reforming for hydrogen production was systematically evaluated. The results indicate that the simultaneous co-precipitation of Al3+ with Cu2+ and Zn2+ leads to partial substitution of Cu-Zn in the basic carbonates by Al3+. This substitution forms a hydrotalcite-like structure and strengthens Zn-Al interactions. On the contrary, after the co-precipitation of Cu2+ and Zn2+, introducing the Al2O3 precursor has a positive effect on eliminating the adverse effects of Al3+ on Cu-Zn substitution in basic carbonates. This process promotes the Cu-ZnO interaction, facilitates the dispersion of CuO species, and enhances the reducibility of catalysts. It also improves the dispersion of Cu on the surface, and ultimately enhanced the catalytic activity. Notably, the catalyst prepared using pseudo-boehmite as the Al2O3 precursor exhibited the highest activity. Under the conditions of a H2O/CH3OH molar ratio of 1.2 and a reaction temperature of 493 K, methanol conversion reached 94.8%, and the H2 space-time yield was 97.5 mol/(kg·h). The catalyst activity remained relatively stable after continuous operation for 25 h. Even after being heat-treated at 723 K for 10 h, the activity loss of the catalyst was only 5.37%.
{"title":"Hydrogen production via steam reforming of methanol on Cu/ZnO/Al2O3 catalysts: Effects of Al2O3 precursors","authors":"HUANG Min , BO Qifei , LI Juan , QIAO Jingxuan , YUAN Shanliang , ZHANG Biao , CHEN Honglin , JIANG Yi","doi":"10.1016/S1872-5813(24)60459-7","DOIUrl":"10.1016/S1872-5813(24)60459-7","url":null,"abstract":"<div><div>A series of Cu/ZnO/Al<sub>2</sub>O<sub>3</sub> catalysts were prepared by co-precipitation method. This research focuses on investigating the influence of different Al<sub>2</sub>O<sub>3</sub> precursors on the catalyst structure through thorough structural characterization techniques. Additionally, the catalytic performance of these catalysts in methanol reforming for hydrogen production was systematically evaluated. The results indicate that the simultaneous co-precipitation of Al<sup>3+</sup> with Cu<sup>2+</sup> and Zn<sup>2+</sup> leads to partial substitution of Cu-Zn in the basic carbonates by Al<sup>3+</sup>. This substitution forms a hydrotalcite-like structure and strengthens Zn-Al interactions. On the contrary, after the co-precipitation of Cu<sup>2+</sup> and Zn<sup>2+</sup>, introducing the Al<sub>2</sub>O<sub>3</sub> precursor has a positive effect on eliminating the adverse effects of Al<sup>3+</sup> on Cu-Zn substitution in basic carbonates. This process promotes the Cu-ZnO interaction, facilitates the dispersion of CuO species, and enhances the reducibility of catalysts. It also improves the dispersion of Cu on the surface, and ultimately enhanced the catalytic activity. Notably, the catalyst prepared using pseudo-boehmite as the Al<sub>2</sub>O<sub>3</sub> precursor exhibited the highest activity. Under the conditions of a H<sub>2</sub>O/CH<sub>3</sub>OH molar ratio of 1.2 and a reaction temperature of 493 K, methanol conversion reached 94.8%, and the H<sub>2</sub> space-time yield was 97.5 mol/(kg·h). The catalyst activity remained relatively stable after continuous operation for 25 h. Even after being heat-treated at 723 K for 10 h, the activity loss of the catalyst was only 5.37%.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 10","pages":"Pages 1443-1453"},"PeriodicalIF":0.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532728","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1016/S1872-5813(24)60458-5
LI Xiuyi, SHEN Haowei, XU Jiale, LI Chunyi
Nano Cr2O3 (n-Cr2O3) was prepared by the thermolysis of the mesoporous Cr-MIL-101, and its catalytic performance for n-hexane dehydrogenation was investigated and compared with Cr2O3 obtained by traditional method. It is found that dehydrogenation of n-hexane on n-Cr2O3 catalyst can produce n-hexenes and benzene efficiently, and the catalytic performance is related to the calcination temperature. The optimal n-hexane conversion can be obtained on n-Cr2O3 calcinated under 600 °C, is 40.6%, and the selectivities to n-hexenes and benzene are 20.1% and 69.3%, respectively. The conversion of n-hexane for n-Cr2O3 catalyst is decreased with calcination temperature increase, while the catalyst stability in dehydrogenation reaction is enhanced. n-Hexane conversion of p-Cr2O3-1 (obtained by precipitation method) and p-Cr2O3-2 (calcinating Cr(NO3)·9H2O directly) catalysts are very low (<7.5%), and their specific activity for n-hexane dehydrogenation are 1.5 and 1.7 g/(m2·h) respectively, lower than that of n-Cr2O3-600 (2.0 g/(m2·h)). The results of BET, XRD, TEM and FT-IR reveal that n-Cr2O3 is the nanoparticles with large specific surface area that more dehydrogenation active sites are exposed, while p-Cr2O3 is the large particles with extremely low surface area that few dehydrogenation active sites are presented. By contrast, industrial Cr2O3/Al2O3 catalyst possesses the highest specific activity of 2.4 g/(m2·h) due to the dispersion effect of Al2O3. Therefore, highly catalytic activity of n-Cr2O3 for n-hexane dehydrogenation is attributed to the unique properties of small particle, large specific surface area and more exposed active sites. This work not only explains the high dehydrogenation activity of nano-Cr2O3 derived by Cr-MIL-101, but also provides guidance for the precise design and synthesis of high-performance CrOx-based catalyst for the dehydrogenation of alkanes.
{"title":"Cr-MIL-101 derived nano Cr2O3 for highly efficient dehydrogenation of n-hexane","authors":"LI Xiuyi, SHEN Haowei, XU Jiale, LI Chunyi","doi":"10.1016/S1872-5813(24)60458-5","DOIUrl":"10.1016/S1872-5813(24)60458-5","url":null,"abstract":"<div><div>Nano Cr<sub>2</sub>O<sub>3</sub> (<em>n</em>-Cr<sub>2</sub>O<sub>3</sub>) was prepared by the thermolysis of the mesoporous Cr-MIL-101, and its catalytic performance for <em>n</em>-hexane dehydrogenation was investigated and compared with Cr<sub>2</sub>O<sub>3</sub> obtained by traditional method. It is found that dehydrogenation of <em>n</em>-hexane on <em>n</em>-Cr<sub>2</sub>O<sub>3</sub> catalyst can produce <em>n</em>-hexenes and benzene efficiently, and the catalytic performance is related to the calcination temperature. The optimal <em>n</em>-hexane conversion can be obtained on <em>n</em>-Cr<sub>2</sub>O<sub>3</sub> calcinated under 600 °C, is 40.6%, and the selectivities to <em>n</em>-hexenes and benzene are 20.1% and 69.3%, respectively. The conversion of <em>n</em>-hexane for <em>n</em>-Cr<sub>2</sub>O<sub>3</sub> catalyst is decreased with calcination temperature increase, while the catalyst stability in dehydrogenation reaction is enhanced. <em>n</em>-Hexane conversion of <em>p</em>-Cr<sub>2</sub>O<sub>3</sub>-1 (obtained by precipitation method) and <em>p</em>-Cr<sub>2</sub>O<sub>3</sub>-2 (calcinating Cr(NO<sub>3</sub>)·9H<sub>2</sub>O directly) catalysts are very low (<7.5%), and their specific activity for <em>n</em>-hexane dehydrogenation are 1.5 and 1.7 g/(m<sup>2</sup>·h) respectively, lower than that of <em>n</em>-Cr<sub>2</sub>O<sub>3</sub>-600 (2.0 g/(m<sup>2</sup>·h)). The results of BET, XRD, TEM and FT-IR reveal that <em>n</em>-Cr<sub>2</sub>O<sub>3</sub> is the nanoparticles with large specific surface area that more dehydrogenation active sites are exposed, while <em>p</em>-Cr<sub>2</sub>O<sub>3</sub> is the large particles with extremely low surface area that few dehydrogenation active sites are presented. By contrast, industrial Cr<sub>2</sub>O<sub>3</sub>/Al<sub>2</sub>O<sub>3</sub> catalyst possesses the highest specific activity of 2.4 g/(m<sup>2</sup>·h) due to the dispersion effect of Al<sub>2</sub>O<sub>3</sub>. Therefore, highly catalytic activity of <em>n</em>-Cr<sub>2</sub>O<sub>3</sub> for <em>n</em>-hexane dehydrogenation is attributed to the unique properties of small particle, large specific surface area and more exposed active sites. This work not only explains the high dehydrogenation activity of nano-Cr<sub>2</sub>O<sub>3</sub> derived by Cr-MIL-101, but also provides guidance for the precise design and synthesis of high-performance CrO<sub><em>x</em></sub>-based catalyst for the dehydrogenation of alkanes.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 10","pages":"Pages 1506-1515"},"PeriodicalIF":0.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532729","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1016/S1872-5813(24)60454-8
ZHANG Jingjing , LING Lixia , MA Caiping , ZHANG Riguang , WANG Baojun
The direct conversion of syngas to ethanol on the RhnNin/TiO2 (n = 1, 2, 3, 4) catalyst has been investigated by using the density functional theory (DFT) and micro-kinetic methods, in order to elucidate the regulatory mechanism of RhnNin alloy cluster size-induced metal-support interaction on the catalytic performance of RhnNin/TiO2 in the ethanol synthesis. The results indicate that Rh1Ni1/TiO2 and Rh3Ni3/TiO2 can significantly enhance the conversion of CO and the formation of C–C bond and meanwhile inhibit the generation of methane. Rh1Ni1/TiO2 exhibits the highest ethanol production activity and relative selectivity. The electronic property analysis results suggest that Ni atoms on the alloy clusters and Ti and O atoms on the supports transfer the most charge to the Rh atoms on the Rh1Ni1/TiO2 catalyst, which displays the strongest Rh-Ni interaction on the alloy clusters as well as the strongest interaction between the alloy clusters and the TiO2 support, endowing Rh1Ni1/TiO2 with the highest catalytic activity. In addition, the Ab-initio molecular dynamics (AIMD) simulations at 525 K show that the Rh1Ni1/TiO2 catalyst has high thermal stability.
利用密度泛函理论（DFT）和微观动力学方法研究了RhnNin/TiO2（n = 1, 2, 3, 4）催化剂将合成气直接转化为乙醇的过程，以阐明RhnNin合金团簇尺寸诱导的金属-支撑相互作用对RhnNin/TiO2在乙醇合成过程中催化性能的调控机制。结果表明，Rh1Ni1/TiO2 和 Rh3Ni3/TiO2 能显著提高 CO 的转化率和 C-C 键的形成，同时抑制甲烷的生成。Rh1Ni1/TiO2 的乙醇生产活性和相对选择性最高。电子性质分析结果表明，Rh1Ni1/TiO2 催化剂中合金团簇上的 Ni 原子以及载体上的 Ti 原子和 O 原子将最多的电荷转移给 Rh 原子，合金团簇上的 Rh-Ni 相互作用最强，合金团簇与 TiO2 载体之间的相互作用也最强，从而赋予 Rh1Ni1/TiO2 最高的催化活性。此外，在 525 K 下进行的 Ab-initio 分子动力学（AIMD）模拟表明，Rh1Ni1/TiO2 催化剂具有很高的热稳定性。
{"title":"Effect of the RhnNin alloy cluster size on the catalytic performance of RhnNin/TiO2 in the conversion of syngas to ethanol","authors":"ZHANG Jingjing , LING Lixia , MA Caiping , ZHANG Riguang , WANG Baojun","doi":"10.1016/S1872-5813(24)60454-8","DOIUrl":"10.1016/S1872-5813(24)60454-8","url":null,"abstract":"<div><div>The direct conversion of syngas to ethanol on the Rh<sub><em>n</em></sub>Ni<sub><em>n</em></sub>/TiO<sub>2</sub> (<em>n</em> = 1, 2, 3, 4) catalyst has been investigated by using the density functional theory (DFT) and micro-kinetic methods, in order to elucidate the regulatory mechanism of Rh<sub><em>n</em></sub>Ni<sub><em>n</em></sub> alloy cluster size-induced metal-support interaction on the catalytic performance of Rh<sub><em>n</em></sub>Ni<sub><em>n</em></sub>/TiO<sub>2</sub> in the ethanol synthesis. The results indicate that Rh<sub>1</sub>Ni<sub>1</sub>/TiO<sub>2</sub> and Rh<sub>3</sub>Ni<sub>3</sub>/TiO<sub>2</sub> can significantly enhance the conversion of CO and the formation of C–C bond and meanwhile inhibit the generation of methane. Rh<sub>1</sub>Ni<sub>1</sub>/TiO<sub>2</sub> exhibits the highest ethanol production activity and relative selectivity. The electronic property analysis results suggest that Ni atoms on the alloy clusters and Ti and O atoms on the supports transfer the most charge to the Rh atoms on the Rh<sub>1</sub>Ni<sub>1</sub>/TiO<sub>2</sub> catalyst, which displays the strongest Rh-Ni interaction on the alloy clusters as well as the strongest interaction between the alloy clusters and the TiO<sub>2</sub> support, endowing Rh<sub>1</sub>Ni<sub>1</sub>/TiO<sub>2</sub> with the highest catalytic activity. In addition, the Ab-initio molecular dynamics (AIMD) simulations at 525 K show that the Rh<sub>1</sub>Ni<sub>1</sub>/TiO<sub>2</sub> catalyst has high thermal stability.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 10","pages":"Pages 1475-1494"},"PeriodicalIF":0.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532727","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1016/S1872-5813(24)60449-4
WANG Han , GUO Shujia , QIN Zhangfeng , LI Zhikai , WANG Guofu , DONG Mei , FAN Weibin , WANG Jianguo
The synthesis of methane from CO and CO2 by hydrogenation is now considered as a promising route in effectively storing hydrogen energy as well as sustainably producing fuels and chemicals, while many reaction details involved in such processes, in particular for the hydrogenation of the CO and CO2 mixture, are not yet adequately understood. As a supplement to our previous works on the hydrogenation of CO and CO2 into alcohols and hydrocarbons, a thermodynamic consideration is made in this work to evaluate the potential and limit for the synthesis of methane from CO, CO2, and their mixture in particular. The results consolidate that in comparison with single CO or CO2, their mixture is probably more credible in practice for the production of methane by hydrogenation, where the overall C-based methane yield can be used as the major index to evaluate the process efficiency. The hydrogenation of CO shows a higher equilibrium yield of methane than the hydrogenation of CO2, while the overall C-based equilibrium yield of methane for the hydrogenation of the CO and CO2 mixture just lies in between and decreases almost lineally with the increase of the CO2/(CO+CO2) molar ratio in the feed, despite the great change in the equilibrium conversions of CO and CO2 with the feed composition. Nevertheless, an adequate overall C-based equilibrium yield of methane (> 85%) can be achieved at a temperature lower than 400 °C and a pressure higher than 0.1 MPa for the stoichiometric hydrogenation of CO, CO2, or their mixture whichever. These results should be beneficial to the design of more efficient catalysts and processes for the hydrogenation of CO/CO2 to methane.
目前，通过加氢从一氧化碳和二氧化碳合成甲烷被认为是有效储存氢能以及可持续生产燃料和化学品的一条很有前途的途径，但人们对此类过程中涉及的许多反应细节，特别是一氧化碳和二氧化碳混合物的加氢反应，还没有充分的了解。作为对我们之前关于将 CO 和 CO2 加氢转化为酒精和碳氢化合物的研究的补充，本研究从热力学角度评估了从 CO、CO2，特别是它们的混合物合成甲烷的潜力和极限。结果表明，与单一的一氧化碳或二氧化碳相比，它们的混合物在通过氢化生产甲烷的实践中可能更可靠，其中以 C 为基础的甲烷总产量可作为评估工艺效率的主要指标。CO 的氢化比 CO2 的氢化显示出更高的甲烷平衡产率，而 CO 和 CO2 混合物氢化的整体 C 基甲烷平衡产率仅介于两者之间，并且随着进料中 CO2/（CO+CO2）摩尔比的增加而几乎直线下降，尽管 CO 和 CO2 的平衡转化率随进料成分的变化而发生很大变化。不过，在温度低于 400 °C 和压力高于 0.1 MPa 的条件下，对 CO、CO2 或它们的混合物进行化学计量加氢，可以获得足够的以 C 为基础的甲烷总平衡产率（85%）。这些结果将有助于设计更高效的催化剂和工艺，将 CO/CO2 加氢转化为甲烷。
{"title":"A thermodynamic consideration on the synthesis of methane from CO, CO2, and their mixture by hydrogenation","authors":"WANG Han , GUO Shujia , QIN Zhangfeng , LI Zhikai , WANG Guofu , DONG Mei , FAN Weibin , WANG Jianguo","doi":"10.1016/S1872-5813(24)60449-4","DOIUrl":"10.1016/S1872-5813(24)60449-4","url":null,"abstract":"<div><div>The synthesis of methane from CO and CO<sub>2</sub> by hydrogenation is now considered as a promising route in effectively storing hydrogen energy as well as sustainably producing fuels and chemicals, while many reaction details involved in such processes, in particular for the hydrogenation of the CO and CO<sub>2</sub> mixture, are not yet adequately understood. As a supplement to our previous works on the hydrogenation of CO and CO<sub>2</sub> into alcohols and hydrocarbons, a thermodynamic consideration is made in this work to evaluate the potential and limit for the synthesis of methane from CO, CO<sub>2</sub>, and their mixture in particular. The results consolidate that in comparison with single CO or CO<sub>2</sub>, their mixture is probably more credible in practice for the production of methane by hydrogenation, where the overall C-based methane yield can be used as the major index to evaluate the process efficiency. The hydrogenation of CO shows a higher equilibrium yield of methane than the hydrogenation of CO<sub>2</sub>, while the overall C-based equilibrium yield of methane for the hydrogenation of the CO and CO<sub>2</sub> mixture just lies in between and decreases almost lineally with the increase of the CO<sub>2</sub>/(CO+CO<sub>2</sub>) molar ratio in the feed, despite the great change in the equilibrium conversions of CO and CO<sub>2</sub> with the feed composition. Nevertheless, an adequate overall C-based equilibrium yield of methane (> 85%) can be achieved at a temperature lower than 400 °C and a pressure higher than 0.1 MPa for the stoichiometric hydrogenation of CO, CO<sub>2</sub>, or their mixture whichever. These results should be beneficial to the design of more efficient catalysts and processes for the hydrogenation of CO/CO<sub>2</sub> to methane.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 10","pages":"Pages 1453-1461"},"PeriodicalIF":0.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-01DOI: 10.1016/S1872-5813(24)60461-5
MA Xiaotong , WANG Zhigang , LU Hao , LIU Wei , WANG Yanxia , ZHAO Jiangshan , SUN Lingmin , YAN Jingchong , ZHUANG Shujuan , LI Huaizhu , KONG Lingxue
Gasification of furfural residue with coal can realize its efficient and clean utilization. But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory. Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study. The effects of furfural residue additions on corrosion of silica brick, corundum brick, high alumina brick and mullite brick were investigated by using XRD, SEM-EDS and Factsage Software, and the corrosion mechanism was analyzed. With increasing furfural residue addition, the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases, while the permeability on silica brick shows a slight decrease trend. Leucite (KAlSi2O6) with high-melting temperature is generated from the reaction of K2O and SiO2 in slag with Al2O3 in refractories after furfural residue is added, which hinders the infiltration of slag in refractories. Kaliophilite (KAlSiO4) of low-melting point is formed when K2O content increases, and this contributes to the infiltration of slag in refractories. The acid-base reaction between slag and silica brick is distinctly occurred, more slag reacts with SiO2 in the silicon brick, resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added. The corrosion of silica brick is mainly caused by the acid-base reaction, while the corrosion of three alumina based refractory bricks of corundum, mullite and high alumina brick is determined by slag infiltration. A linear correlation between the percolation rate and slag viscosity is established, the slag permeability increases with decreasing viscosity, resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.
{"title":"Corrosion behavior of co-gasification slag of furfural residue and coal on alumina-silica refractories","authors":"MA Xiaotong , WANG Zhigang , LU Hao , LIU Wei , WANG Yanxia , ZHAO Jiangshan , SUN Lingmin , YAN Jingchong , ZHUANG Shujuan , LI Huaizhu , KONG Lingxue","doi":"10.1016/S1872-5813(24)60461-5","DOIUrl":"10.1016/S1872-5813(24)60461-5","url":null,"abstract":"<div><div>Gasification of furfural residue with coal can realize its efficient and clean utilization. But the high alkali metal content in furfural slag is easy to cause the corrosion of gasifier refractory. Two gasification coals with different silica alumina ratio and a furfural residue were selected in the study. The effects of furfural residue additions on corrosion of silica brick, corundum brick, high alumina brick and mullite brick were investigated by using XRD, SEM-EDS and Factsage Software, and the corrosion mechanism was analyzed. With increasing furfural residue addition, the permeability of the slags to high-aluminium-bearing refractories first decreases and then increases, while the permeability on silica brick shows a slight decrease trend. Leucite (KAlSi<sub>2</sub>O<sub>6</sub>) with high-melting temperature is generated from the reaction of K<sub>2</sub>O and SiO<sub>2</sub> in slag with Al<sub>2</sub>O<sub>3</sub> in refractories after furfural residue is added, which hinders the infiltration of slag in refractories. Kaliophilite (KAlSiO<sub>4</sub>) of low-melting point is formed when K<sub>2</sub>O content increases, and this contributes to the infiltration of slag in refractories. The acid-base reaction between slag and silica brick is distinctly occurred, more slag reacts with SiO<sub>2</sub> in the silicon brick, resulting in a decrease in the amount of slag infiltrating into the silicon brick as furfural residue is added. The corrosion of silica brick is mainly caused by the acid-base reaction, while the corrosion of three alumina based refractory bricks of corundum, mullite and high alumina brick is determined by slag infiltration. A linear correlation between the percolation rate and slag viscosity is established, the slag permeability increases with decreasing viscosity, resulting in stronger permeability for the high Si/Al ratio slag with lower viscosity.</div></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 10","pages":"Pages 1387-1397"},"PeriodicalIF":0.0,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142532730","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-01DOI: 10.1016/S1872-5813(24)60453-4
ZHANG Tongtong , ZHU Huihui , ZHU Yaming , HU Chaoshuai , LÜ Jun , CHENG Junxia , BAI Yonghui , ZHAO Xuefei
Ethylene residue pitch (ETP, the heavy component in ethylene residue tar) is widely used as a preferred raw material for preparing petroleum-based artificial carbon materials characterized by high carbon content, high aromaticity, and low heteroatom (S, N) content. To investigate the coking properties of ETP, eight components of ETP (four soluble and four insoluble components) were obtained via extraction and separation using methanol, n-butanol, n-hexane, and dimethyl sulfoxide as solvents. The thermal conversion (temperature = 500 °C) and carbonization treatment (temperature =1400 °C) were carried out on each pitch component. The basic physical properties of ETP components were observed using infrared spectroscopy, thermogravimetric analysis, and 1H-NMR. The microstructure of the petroleum-based pitch coke was studied using polarizing microscopy, X-ray single crystal diffraction (XRD), Raman spectroscopy, and scanning electron microscopy. The aromaticity of the insoluble components in ETP was slightly higher than that of soluble components, and the insoluble components had slightly fewer branching chains than those in soluble components. The microstrength of the ETP coke obtained using insoluble components was higher than that obtained using soluble components, and the true density of ETP coke HS-C was as high as 2.0554 g/cm3.
{"title":"Investigating the coking performance of ethylene residue pitch components","authors":"ZHANG Tongtong , ZHU Huihui , ZHU Yaming , HU Chaoshuai , LÜ Jun , CHENG Junxia , BAI Yonghui , ZHAO Xuefei","doi":"10.1016/S1872-5813(24)60453-4","DOIUrl":"10.1016/S1872-5813(24)60453-4","url":null,"abstract":"<div><p>Ethylene residue pitch (ETP, the heavy component in ethylene residue tar) is widely used as a preferred raw material for preparing petroleum-based artificial carbon materials characterized by high carbon content, high aromaticity, and low heteroatom (S, N) content. To investigate the coking properties of ETP, eight components of ETP (four soluble and four insoluble components) were obtained via extraction and separation using methanol, <em>n</em>-butanol, <em>n</em>-hexane, and dimethyl sulfoxide as solvents. The thermal conversion (temperature = 500 °C) and carbonization treatment (temperature =1400 °C) were carried out on each pitch component. The basic physical properties of ETP components were observed using infrared spectroscopy, thermogravimetric analysis, and <sup>1</sup>H-NMR. The microstructure of the petroleum-based pitch coke was studied using polarizing microscopy, X-ray single crystal diffraction (XRD), Raman spectroscopy, and scanning electron microscopy. The aromaticity of the insoluble components in ETP was slightly higher than that of soluble components, and the insoluble components had slightly fewer branching chains than those in soluble components. The microstrength of the ETP coke obtained using insoluble components was higher than that obtained using soluble components, and the true density of ETP coke HS-C was as high as 2.0554 g/cm<sup>3</sup>.</p></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 9","pages":"Pages 1348-1360"},"PeriodicalIF":0.0,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142164372","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-01DOI: 10.1016/S1872-5813(24)60452-4
HE Zhanjun , GONG Kun , DAI Yuanyuan , NIU Qiang , LIN Tiejun , ZHONG Liangshu
Ni/TiO2 catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO2 remains unclear. In this work, the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO2. Structural characterizations revealed that a distinct TiOx coating on the Ni nanoparticles (NPs) was evident for Ni/TiO2-700 catalyst due to strong metal-support interaction. It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased, thereby enhancing the exposure of Ni active sites. The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4, which led to the much elevated catalytic activity for Ni/ TiO2-950 in which rutile dominated. Therefore, the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio. Ni/TiO2-950, characterized by a predominant rutile phase, exhibited the highest DRM reactivity, with remarkable H2 and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h), respectively. These rates were approximately 257 and 130 times higher, respectively, compared to those obtained on Ni/TiO2-700 with anatase. This study suggests that the optimization of crystal structure of TiO2 support can effectively enhance the performance of photothermal DRM reaction.
{"title":"Regulating crystal phase of TiO2 to enhance catalytic activity of Ni/TiO2 for solar-driven dry reforming of methane","authors":"HE Zhanjun , GONG Kun , DAI Yuanyuan , NIU Qiang , LIN Tiejun , ZHONG Liangshu","doi":"10.1016/S1872-5813(24)60452-4","DOIUrl":"10.1016/S1872-5813(24)60452-4","url":null,"abstract":"<div><p>Ni/TiO<sub>2</sub> catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO<sub>2</sub> remains unclear. In this work, the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO<sub>2</sub>. Structural characterizations revealed that a distinct TiO<sub><em>x</em></sub> coating on the Ni nanoparticles (NPs) was evident for Ni/TiO<sub>2</sub>-700 catalyst due to strong metal-support interaction. It is observed that the TiO<sub><em>x</em></sub> overlayer gradually disappeared as the ratio of rutile/anatase increased, thereby enhancing the exposure of Ni active sites. The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH<sub>4</sub>, which led to the much elevated catalytic activity for Ni/ TiO<sub>2</sub>-950 in which rutile dominated. Therefore, the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio. Ni/TiO<sub>2</sub>-950, characterized by a predominant rutile phase, exhibited the highest DRM reactivity, with remarkable H<sub>2</sub> and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h), respectively. These rates were approximately 257 and 130 times higher, respectively, compared to those obtained on Ni/TiO<sub>2</sub>-700 with anatase. This study suggests that the optimization of crystal structure of TiO<sub>2</sub> support can effectively enhance the performance of photothermal DRM reaction.</p></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 9","pages":"Pages 1203-1213"},"PeriodicalIF":0.0,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142163666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-09-01DOI: 10.1016/S1872-5813(24)60455-X
YUAN Zhiguo , ZHANG Fan , YANG Shili , XU Xiaoying , LIU Chenyang , QIU Zhengpu , WEI Wei
The complex conditions of methanol production from coke-oven gas have brought challenges to the copper-based methanol synthesis catalyst. In this work, a series of zinc-malachite samples with different Mg contents were prepared. The zinc-malachite and calcined samples were characterized by in-situ X-ray diffraction (XRD), thermogravimetry-mass spectrometry (TG-MS), N2 physical adsorption, H2 programmed temperature reduction (H2-TPR), CO2 programmed temperature desorption (CO2-TPD) and other methods. The effects of Mg addition on the structure of zinc-malachite and its catalytic performance of methanol synthesis were investigated. The results showed that the addition of Mg increased the degree of Cu substitution inside the zinc-malachite structure and promoted the formation of high temperature carbonates in the catalyst after roasting. With the increase of Mg content, the specific surface area of the calcined catalyst increased gradually, and the Cu grain size decreased simultaneously. In-situ XRD results showed that a small amount of Mg could effectively inhibit the growth of copper grain size during the heat treatment. The evaluation showed that the initial activity of the catalyst increased first and then decreased with Mg addition, and the activity of the Mg-doped catalyst remained at a relatively high level after heat treatment. The appropriate Mg addition is beneficial to the initial activity and thermal stability of Cu-based methanol synthesis catalyst.
{"title":"Effect of Mg modification on the catalytic performance of zinc malachite for methanol synthesis","authors":"YUAN Zhiguo , ZHANG Fan , YANG Shili , XU Xiaoying , LIU Chenyang , QIU Zhengpu , WEI Wei","doi":"10.1016/S1872-5813(24)60455-X","DOIUrl":"10.1016/S1872-5813(24)60455-X","url":null,"abstract":"<div><p>The complex conditions of methanol production from coke-oven gas have brought challenges to the copper-based methanol synthesis catalyst. In this work, a series of zinc-malachite samples with different Mg contents were prepared. The zinc-malachite and calcined samples were characterized by <em>in-situ</em> X-ray diffraction (XRD), thermogravimetry-mass spectrometry (TG-MS), N<sub>2</sub> physical adsorption, H<sub>2</sub> programmed temperature reduction (H<sub>2</sub>-TPR), CO<sub>2</sub> programmed temperature desorption (CO<sub>2</sub>-TPD) and other methods. The effects of Mg addition on the structure of zinc-malachite and its catalytic performance of methanol synthesis were investigated. The results showed that the addition of Mg increased the degree of Cu substitution inside the zinc-malachite structure and promoted the formation of high temperature carbonates in the catalyst after roasting. With the increase of Mg content, the specific surface area of the calcined catalyst increased gradually, and the Cu grain size decreased simultaneously. <em>In-situ</em> XRD results showed that a small amount of Mg could effectively inhibit the growth of copper grain size during the heat treatment. The evaluation showed that the initial activity of the catalyst increased first and then decreased with Mg addition, and the activity of the Mg-doped catalyst remained at a relatively high level after heat treatment. The appropriate Mg addition is beneficial to the initial activity and thermal stability of Cu-based methanol synthesis catalyst.</p></div>","PeriodicalId":15956,"journal":{"name":"燃料化学学报","volume":"52 9","pages":"Pages 1249-1255"},"PeriodicalIF":0.0,"publicationDate":"2024-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S187258132460455X/pdf?md5=4b9a6e1d688f9e9c3a399a64629a322f&pid=1-s2.0-S187258132460455X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142163669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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