Pub Date : 1996-08-01DOI: 10.1080/01614949608006461
G. Tembe, A. R. Bandyopadhyay, P. A. Ganeshpure, S. Satish
Abstract The review deals with the chemistry of dimerization of acrylic esters in the presence of various catalysts. The article covers literature from 1963 through early 1995. The dimerization reactions are divided into three categories depending on the type of catalyst used, namely, phosphine-catalyzed, metal-catalyzed, and miscellaneous catalysts. Phosphine catalyzed dimerization leads to branched or head—tail dimers. Metal catalyzed dimerization deals with the reactions that take place in the coordination sphere of the transition metals (Ni, Pd, Ru, and Rh) complexes and are aimed at linear or tail—tail dimers. The tail—tail dimers, dialkyl hexenedioates, have a commercial potential as precursors of adipic acid, which is a raw material in the manufacture of nylon-6,6. Various strategies involved in designing the transition metal catalysts for tail—tail dimerization are highlighted. A miscellaneous catalyst section deals with systems that are not covered under the above two categories. It describes cat...
{"title":"Catalytic Dimerization of Alkyl Acrylates","authors":"G. Tembe, A. R. Bandyopadhyay, P. A. Ganeshpure, S. Satish","doi":"10.1080/01614949608006461","DOIUrl":"https://doi.org/10.1080/01614949608006461","url":null,"abstract":"Abstract The review deals with the chemistry of dimerization of acrylic esters in the presence of various catalysts. The article covers literature from 1963 through early 1995. The dimerization reactions are divided into three categories depending on the type of catalyst used, namely, phosphine-catalyzed, metal-catalyzed, and miscellaneous catalysts. Phosphine catalyzed dimerization leads to branched or head—tail dimers. Metal catalyzed dimerization deals with the reactions that take place in the coordination sphere of the transition metals (Ni, Pd, Ru, and Rh) complexes and are aimed at linear or tail—tail dimers. The tail—tail dimers, dialkyl hexenedioates, have a commercial potential as precursors of adipic acid, which is a raw material in the manufacture of nylon-6,6. Various strategies involved in designing the transition metal catalysts for tail—tail dimerization are highlighted. A miscellaneous catalyst section deals with systems that are not covered under the above two categories. It describes cat...","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"74 1","pages":"299-327"},"PeriodicalIF":10.9,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79976736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1996-08-01DOI: 10.1080/01614949608006462
Xuemin Song, A. Sayari
Abstract This review article deals with recent progress in the preparation of sulfated zirconia (SZ)-bassed, strong solid-acid catalysts, the characterization of their physicochemical properties and the evaluation of their catalytic performance in various promising applications. Strong emphasis was put on discussion of controversial issues such as the strength of acid sites, the nature of active sites, the reaction mechanism, and the role and state of supported platinum. An important part of this work was devoted to recent catalytic applications.
{"title":"Sulfated Zirconia-Based Strong Solid-Acid Catalysts: Recent Progress","authors":"Xuemin Song, A. Sayari","doi":"10.1080/01614949608006462","DOIUrl":"https://doi.org/10.1080/01614949608006462","url":null,"abstract":"Abstract This review article deals with recent progress in the preparation of sulfated zirconia (SZ)-bassed, strong solid-acid catalysts, the characterization of their physicochemical properties and the evaluation of their catalytic performance in various promising applications. Strong emphasis was put on discussion of controversial issues such as the strength of acid sites, the nature of active sites, the reaction mechanism, and the role and state of supported platinum. An important part of this work was devoted to recent catalytic applications.","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"43 8 Pt 1 1","pages":"329-412"},"PeriodicalIF":10.9,"publicationDate":"1996-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"82685489","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1996-05-01DOI: 10.1080/01614949608006458
In-Soo Park∗, D. Do, A. Rodrigues
Introduction There has been a vast amount of investigation in the field of experimental and theoretical treatments of the effective diffusivity in porous media for more than half of a century [1-4]. The effective diffusivity is required for several reasons [5]; for example, during catalyst formulation, active species can be laid down precisely or with specified concentration profiles on a porous matrix or support. In experimental work on heterogeneous reactions an effective diffusivity is needed to obtain the value of the Thiele modulus and hence to determine the intrinsic reaction kinetics. In reactor design the diffusivity is needed to evaluate the Thiele modulus, which can then be an aid in predicting reaction rates for heterogeneous systems. In addition, a simple and quick testing method could be used as a screening or quality control procedure during catalyst manufacture. ∗ On leave from the Department of Chemical Engineering, Kyungnam University, Masan 631-701, Korea.
{"title":"Measurement of the Effective Diffusivity in Porous Media by the Diffusion Cell Method","authors":"In-Soo Park∗, D. Do, A. Rodrigues","doi":"10.1080/01614949608006458","DOIUrl":"https://doi.org/10.1080/01614949608006458","url":null,"abstract":"Introduction There has been a vast amount of investigation in the field of experimental and theoretical treatments of the effective diffusivity in porous media for more than half of a century [1-4]. The effective diffusivity is required for several reasons [5]; for example, during catalyst formulation, active species can be laid down precisely or with specified concentration profiles on a porous matrix or support. In experimental work on heterogeneous reactions an effective diffusivity is needed to obtain the value of the Thiele modulus and hence to determine the intrinsic reaction kinetics. In reactor design the diffusivity is needed to evaluate the Thiele modulus, which can then be an aid in predicting reaction rates for heterogeneous systems. In addition, a simple and quick testing method could be used as a screening or quality control procedure during catalyst manufacture. ∗ On leave from the Department of Chemical Engineering, Kyungnam University, Masan 631-701, Korea.","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"53 1","pages":"189-247"},"PeriodicalIF":10.9,"publicationDate":"1996-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84767284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1996-05-01DOI: 10.1080/01614949608006457
P. T. Vasudevan, J. Fierro
Introduction The increasing importance of hydrodesulfurization (HDS) in petroleum processing in order to produce clean-burning fuels has led to a surge of research on the chemistry and engineering of HDS. Most of the earlier works are focused on catalyst characterization by physical methods; on low-pressure reaction studies of compounds like thiophene having relatively high reactivities; on process development; or on CoMo, NiMo, or NiW catalysts supported on alumina, often doped by fluorine or phosphorus. Almost all the reviews have concentrated on alumina-supported CoMo, NiMo, and NiW sulfide catalysts for hydrotreating. Even reviews that are not limited to the above catalytic systems essentially deal with studies of simple compounds like thiophene.
{"title":"A review of deep hydrodesulfurization catalysis","authors":"P. T. Vasudevan, J. Fierro","doi":"10.1080/01614949608006457","DOIUrl":"https://doi.org/10.1080/01614949608006457","url":null,"abstract":"Introduction The increasing importance of hydrodesulfurization (HDS) in petroleum processing in order to produce clean-burning fuels has led to a surge of research on the chemistry and engineering of HDS. Most of the earlier works are focused on catalyst characterization by physical methods; on low-pressure reaction studies of compounds like thiophene having relatively high reactivities; on process development; or on CoMo, NiMo, or NiW catalysts supported on alumina, often doped by fluorine or phosphorus. Almost all the reviews have concentrated on alumina-supported CoMo, NiMo, and NiW sulfide catalysts for hydrotreating. Even reviews that are not limited to the above catalytic systems essentially deal with studies of simple compounds like thiophene.","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"1 1","pages":"161-188"},"PeriodicalIF":10.9,"publicationDate":"1996-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88204556","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1996-05-01DOI: 10.1080/01614949608006459
L. Guczi, V. Santen, K. Sharma
Introduction Methane is the main component of natural gas and its utilization amounts to ca. 1.7 × 109 tons of oil equivalent per year [1]. Since the present reserve of methane is located in remote places, its transportation is a major problem. Methane coupling to form C2+ hydrocarbons is, therefore, of a primary importance because before transportation methane should be converted into hydrocarbons with higher boiling points, such as ethane, propane, etc. The catalytic conversion of methane can be carried out in several ways which have excellently been reviewed in Refs. 1 and 2. Basically, three routes exist: (i) the indirect route in which methane is first converted into syngas in presence of water (steam reforming), CO2 (carbon dioxide reforming), or oxygen (partial oxidation) and the resultant syngas can be utilized in the traditional way; (ii) direct coupling in the presence of oxygen (oxidative coupling of methane, OCM) or hydrogen (two-step polymerization); and (iii) direct conversion in the presenc...
{"title":"Low-temperature coupling of methane","authors":"L. Guczi, V. Santen, K. Sharma","doi":"10.1080/01614949608006459","DOIUrl":"https://doi.org/10.1080/01614949608006459","url":null,"abstract":"Introduction Methane is the main component of natural gas and its utilization amounts to ca. 1.7 × 109 tons of oil equivalent per year [1]. Since the present reserve of methane is located in remote places, its transportation is a major problem. Methane coupling to form C2+ hydrocarbons is, therefore, of a primary importance because before transportation methane should be converted into hydrocarbons with higher boiling points, such as ethane, propane, etc. The catalytic conversion of methane can be carried out in several ways which have excellently been reviewed in Refs. 1 and 2. Basically, three routes exist: (i) the indirect route in which methane is first converted into syngas in presence of water (steam reforming), CO2 (carbon dioxide reforming), or oxygen (partial oxidation) and the resultant syngas can be utilized in the traditional way; (ii) direct coupling in the presence of oxygen (oxidative coupling of methane, OCM) or hydrogen (two-step polymerization); and (iii) direct conversion in the presenc...","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"33 1","pages":"249-296"},"PeriodicalIF":10.9,"publicationDate":"1996-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80386004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1996-02-01DOI: 10.1080/01614949608006453
Y. Matros, G. Bunimovich
Introduction Transition from the usual steady-state mode of continuous processes toward forced unsteady-state conditions (FUSC) has been discussed in chemical engineering literature since the beginning of the 1960s [1-12]. FUSC can be created by periodic variations of temperature, composition, or other parameters to the inlet of a chemical unit.
{"title":"Reverse-Flow Operation in Fixed Bed Catalytic Reactors","authors":"Y. Matros, G. Bunimovich","doi":"10.1080/01614949608006453","DOIUrl":"https://doi.org/10.1080/01614949608006453","url":null,"abstract":"Introduction Transition from the usual steady-state mode of continuous processes toward forced unsteady-state conditions (FUSC) has been discussed in chemical engineering literature since the beginning of the 1960s [1-12]. FUSC can be created by periodic variations of temperature, composition, or other parameters to the inlet of a chemical unit.","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"71 1","pages":"1-68"},"PeriodicalIF":10.9,"publicationDate":"1996-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86341605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1996-02-01DOI: 10.1080/01614949608006455
K. A. Cumming, B. Wojciechowski
Introduction Understanding of the process of hydrogen redistribution in catalytic cracking has long been recognized as essential to understanding of the coking processes responsible for catalyst decay. Hydrogen redistribution is also thought to be behind the puzzling excess of paraffins over olefins that has been noted by several authors [1-3], and to hold the key to determining the selectivity of cracking reactions. If the transfer of hydrogen during catalytic cracking can be understood and quantified, much of the detail of the overall process should become clear.
{"title":"Hydrogen Transfer, Coke Formation, and Catalyst Decay and Their Role in the Chain Mechanism of Catalytic Cracking","authors":"K. A. Cumming, B. Wojciechowski","doi":"10.1080/01614949608006455","DOIUrl":"https://doi.org/10.1080/01614949608006455","url":null,"abstract":"Introduction Understanding of the process of hydrogen redistribution in catalytic cracking has long been recognized as essential to understanding of the coking processes responsible for catalyst decay. Hydrogen redistribution is also thought to be behind the puzzling excess of paraffins over olefins that has been noted by several authors [1-3], and to hold the key to determining the selectivity of cracking reactions. If the transfer of hydrogen during catalytic cracking can be understood and quantified, much of the detail of the overall process should become clear.","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"27 1","pages":"101-157"},"PeriodicalIF":10.9,"publicationDate":"1996-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87266504","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1996-02-01DOI: 10.1080/01614949608006454
B. Delmon, G. Froment
Introduction Evidence has accumulated in the last 20 years that spillover processes play a crucial role in many catalytic phenomena. Four symposia have highlighted the advances of knowledge in this area, and the progressive recognition that the phenomena have extremely important consequences (Delmon et al., 1973; Inui et al., 1993; Pajonk et al., 1983; Steinberg, 1989). In spite of this, very few kinetic models incorporating spillover have been presented. Little attention, if any, is given to these phenomena in the design of processes or in the definition of operating conditions. ∗Review based on a lecture presented at the 13th Colloquim on Chemical Reaction Engineering (13 CCRE), held in Windsor Castle, U.K., and jointly organized by the Working Parties “Chemical Reaction Engineering” and “Chemical Engineering in the Applications of Catalysis” of the European Federation of Chemical Engineering.
在过去20年中积累的证据表明，溢出过程在许多催化现象中起着至关重要的作用。四次专题讨论会强调了这一领域知识的进步，并逐渐认识到这些现象具有极其重要的后果(Delmon et al.， 1973;Inui等人，1993年;Pajonk et al.， 1983;斯坦伯格,1989)。尽管如此，很少有包含溢出的动力学模型被提出。在工艺设计或操作条件的定义中，很少注意到这些现象。*基于在英国温莎城堡举行的第13届化学反应工程研讨会(13 CCRE)上的演讲，该研讨会由欧洲化学工程联合会“化学反应工程”和“化学工程在催化应用中的应用”工作组联合组织。
{"title":"Remote control of catalytic sites by spillover species: A chemical reaction engineering approach","authors":"B. Delmon, G. Froment","doi":"10.1080/01614949608006454","DOIUrl":"https://doi.org/10.1080/01614949608006454","url":null,"abstract":"Introduction Evidence has accumulated in the last 20 years that spillover processes play a crucial role in many catalytic phenomena. Four symposia have highlighted the advances of knowledge in this area, and the progressive recognition that the phenomena have extremely important consequences (Delmon et al., 1973; Inui et al., 1993; Pajonk et al., 1983; Steinberg, 1989). In spite of this, very few kinetic models incorporating spillover have been presented. Little attention, if any, is given to these phenomena in the design of processes or in the definition of operating conditions. ∗Review based on a lecture presented at the 13th Colloquim on Chemical Reaction Engineering (13 CCRE), held in Windsor Castle, U.K., and jointly organized by the Working Parties “Chemical Reaction Engineering” and “Chemical Engineering in the Applications of Catalysis” of the European Federation of Chemical Engineering.","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"10 1","pages":"69-100"},"PeriodicalIF":10.9,"publicationDate":"1996-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74684648","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1995-11-01DOI: 10.1080/01614949508006451
R. A. Santen, M. Neurock
Introduction A. General The heart of many commercial catalytic processes involves chemistry on transition metal particles and surfaces. The success in designing active surface ensembles, promoters, and selective poisons is inevitably tied to our knowledge of the fundamental principles which control transition metal surface chemistry. One extreme would be the rigorous description and energetic predictions for each elementary reaction step of an entire catalytic cycle from first-principle theoretical methods. While desirable, this has to date been an unattainable goal due to the limitations in both raw computer (CPU) requirements and the accuracy of the available computational methods. Recent advances in both quantum-chemical methods and computational resources, however, are driving this goal closer to reality. Theoretical treatments of adsorbate-surface interactions have rapidly advanced to the stage where detailed understandings of the governing structural and electronic features are readily available. In...
{"title":"Concepts in Theoretical Heterogeneous Catalytic Reactivity","authors":"R. A. Santen, M. Neurock","doi":"10.1080/01614949508006451","DOIUrl":"https://doi.org/10.1080/01614949508006451","url":null,"abstract":"Introduction A. General The heart of many commercial catalytic processes involves chemistry on transition metal particles and surfaces. The success in designing active surface ensembles, promoters, and selective poisons is inevitably tied to our knowledge of the fundamental principles which control transition metal surface chemistry. One extreme would be the rigorous description and energetic predictions for each elementary reaction step of an entire catalytic cycle from first-principle theoretical methods. While desirable, this has to date been an unattainable goal due to the limitations in both raw computer (CPU) requirements and the accuracy of the available computational methods. Recent advances in both quantum-chemical methods and computational resources, however, are driving this goal closer to reality. Theoretical treatments of adsorbate-surface interactions have rapidly advanced to the stage where detailed understandings of the governing structural and electronic features are readily available. In...","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"38 1","pages":"557-698"},"PeriodicalIF":10.9,"publicationDate":"1995-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74079502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 1995-11-01DOI: 10.1080/01614949508006450
M. Schneider, A. Baiker
Introduction Aerogels offer interesting opportunities for catalysis due to their unique morphological and chemical properties. These properties originate from their wet-chemical preparation by the solution-sol-gel (SSG) method and their subsequent liberation from the solvent via critical-point drying or supercritical (or hypercritical) drying (SCD). Due to the “structure-preserving” ability of SCD, the usually oxidic (or metallic) aerogels are solids of high porosity and specific surface area.
{"title":"Aerogels in catalysis","authors":"M. Schneider, A. Baiker","doi":"10.1080/01614949508006450","DOIUrl":"https://doi.org/10.1080/01614949508006450","url":null,"abstract":"Introduction Aerogels offer interesting opportunities for catalysis due to their unique morphological and chemical properties. These properties originate from their wet-chemical preparation by the solution-sol-gel (SSG) method and their subsequent liberation from the solvent via critical-point drying or supercritical (or hypercritical) drying (SCD). Due to the “structure-preserving” ability of SCD, the usually oxidic (or metallic) aerogels are solids of high porosity and specific surface area.","PeriodicalId":50986,"journal":{"name":"Catalysis Reviews-Science and Engineering","volume":"1 1","pages":"515-556"},"PeriodicalIF":10.9,"publicationDate":"1995-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73324454","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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