Carbon dioxide capture,utilization and storage(CCUS)eincluding conversion to valuable chemicals-is a challenging contemporary issue having multi-facets.The prospect to utilize carbon dioxide(CO_(2))as a feedstock for ...Carbon dioxide capture,utilization and storage(CCUS)eincluding conversion to valuable chemicals-is a challenging contemporary issue having multi-facets.The prospect to utilize carbon dioxide(CO_(2))as a feedstock for synthetic applications in chemical and fuel industries-through carboxylation and reduction reactions-is the subject of this review.Current statute of the heterogeneously catalyzed hydrogenation,as well as the photocatalytic and electrocatalytic activations of conversion of CO_(2) to value-added chemicals is overviewed.Envisaging CO_(2) as a viable alternative to natural gas and oil as carbon resource for the chemical supply chain,three stages of development;namely,(i)existing mature technologies(such as urea production),(ii)emerging technologies(such as formic acid or other single carbon(C1)chemicals manufacture)and(iii)innovative explorations(such as electrocatalytic ethylene production)have been identified and highlighted.A unique aspect of this review is the exploitations of reactions of CO2 ewhich stems from existing petrochemical plants-with the commodity petrochemicals(such as,methanol,ethylene and ethylene oxide)produced at the same or nearby complex in order to obtain value-added products while contributing also to CO_(2) fixation simultaneously.Exemplifying worldwide ethylene oxide facilities,it is recognized that they produce about 3 million tons of CO2 annually.Such a CO_(2) resource,which is already separated in pure form as a requirement of the process,should best be converted to a value-added chemical there avoiding current practice of discharging to the atmosphere.The potential utilization of CO_(2),captured at power plants,should also been taken into consideration for sustainability.This CO_(2) source,which is potentially a raw material for the chemical industry,will be available at sufficient quality and at gigantic quantity upon realization of on-going tangible capture projects.Products resulting from carboxylation reactions are obvious conversions.In addition,provided that enough supply of energy from non-fossil resources,such as solar[1],is ensured,CO_(2) reduction reactions can produce several valuable commodity chemicals including multi-carbon compounds,such as ethylene and acrylic acid,in addition to C1 chemicals and polymers.Presently,there are only few developing technologies which can find industrial applications.Therefore,there is a need for concerted research in order to assess the viability of these promising exploratory technologies rationally.展开更多
Amines are well-known for their reversible reactions with CO_(2),which make them ideal for CO_(2) capture from several gas streams,including flue gas.In this respect,selective CO_(2) absorption by aqueous alkanolamine...Amines are well-known for their reversible reactions with CO_(2),which make them ideal for CO_(2) capture from several gas streams,including flue gas.In this respect,selective CO_(2) absorption by aqueous alkanolamines is the most mature technology but the process is energy intensive and has also corrosion problems.Both disadvantages can be diminished to a certain extent by chemical adsorption of CO_(2) selectively.The most important element of the chemical adsorption of CO_(2) involves the design and development of a suitable adsorbent which consist of a porous support onto which an amine is attached or immobilized.Such an adsorbent is often called as solid amine sorbent.This review covers solid amine-based studies which are developed and published in recent years.First,the review examines several different types of porous support materials,namely,three mesoporous silica(MCM-41,SBA-15 and KIT-6)and two polymeric supports(PMMA and PS)for CO_(2) adsorption.Emphasis is given to the synthesis,modifications and characterizations-such as BET and PXRD data-of them.Amination of these supports to obtain a solid amine sorbent through impregnation or grafting is reviewed comparatively.Focus is given to the adsorption mechanisms,material characteristics,and synthesis methods which are discussed in detail.Significant amount of original data are also presented which makes this review unique.Finally,relevant CO_(2) adsorption(or equilibrium)capacity data,and cyclic adsorption/desorption performance and stability of important classes of solid amine sorbents are critically reviewed.These include severa PEI or TEPA impregnated adsorbents and APTES-grafted systems.展开更多
基金Authors gratefully acknowledge Hasan Arslan,Senior Process Consultant,PTTGC America,for the hindsight provided for matured and developing petrochemical processes.
文摘Carbon dioxide capture,utilization and storage(CCUS)eincluding conversion to valuable chemicals-is a challenging contemporary issue having multi-facets.The prospect to utilize carbon dioxide(CO_(2))as a feedstock for synthetic applications in chemical and fuel industries-through carboxylation and reduction reactions-is the subject of this review.Current statute of the heterogeneously catalyzed hydrogenation,as well as the photocatalytic and electrocatalytic activations of conversion of CO_(2) to value-added chemicals is overviewed.Envisaging CO_(2) as a viable alternative to natural gas and oil as carbon resource for the chemical supply chain,three stages of development;namely,(i)existing mature technologies(such as urea production),(ii)emerging technologies(such as formic acid or other single carbon(C1)chemicals manufacture)and(iii)innovative explorations(such as electrocatalytic ethylene production)have been identified and highlighted.A unique aspect of this review is the exploitations of reactions of CO2 ewhich stems from existing petrochemical plants-with the commodity petrochemicals(such as,methanol,ethylene and ethylene oxide)produced at the same or nearby complex in order to obtain value-added products while contributing also to CO_(2) fixation simultaneously.Exemplifying worldwide ethylene oxide facilities,it is recognized that they produce about 3 million tons of CO2 annually.Such a CO_(2) resource,which is already separated in pure form as a requirement of the process,should best be converted to a value-added chemical there avoiding current practice of discharging to the atmosphere.The potential utilization of CO_(2),captured at power plants,should also been taken into consideration for sustainability.This CO_(2) source,which is potentially a raw material for the chemical industry,will be available at sufficient quality and at gigantic quantity upon realization of on-going tangible capture projects.Products resulting from carboxylation reactions are obvious conversions.In addition,provided that enough supply of energy from non-fossil resources,such as solar[1],is ensured,CO_(2) reduction reactions can produce several valuable commodity chemicals including multi-carbon compounds,such as ethylene and acrylic acid,in addition to C1 chemicals and polymers.Presently,there are only few developing technologies which can find industrial applications.Therefore,there is a need for concerted research in order to assess the viability of these promising exploratory technologies rationally.
基金This work has been supported by Turkish Scientific and Technological Research Council(Project Number:111A016).Authors gratefully acknowledge the financial support.
文摘Amines are well-known for their reversible reactions with CO_(2),which make them ideal for CO_(2) capture from several gas streams,including flue gas.In this respect,selective CO_(2) absorption by aqueous alkanolamines is the most mature technology but the process is energy intensive and has also corrosion problems.Both disadvantages can be diminished to a certain extent by chemical adsorption of CO_(2) selectively.The most important element of the chemical adsorption of CO_(2) involves the design and development of a suitable adsorbent which consist of a porous support onto which an amine is attached or immobilized.Such an adsorbent is often called as solid amine sorbent.This review covers solid amine-based studies which are developed and published in recent years.First,the review examines several different types of porous support materials,namely,three mesoporous silica(MCM-41,SBA-15 and KIT-6)and two polymeric supports(PMMA and PS)for CO_(2) adsorption.Emphasis is given to the synthesis,modifications and characterizations-such as BET and PXRD data-of them.Amination of these supports to obtain a solid amine sorbent through impregnation or grafting is reviewed comparatively.Focus is given to the adsorption mechanisms,material characteristics,and synthesis methods which are discussed in detail.Significant amount of original data are also presented which makes this review unique.Finally,relevant CO_(2) adsorption(or equilibrium)capacity data,and cyclic adsorption/desorption performance and stability of important classes of solid amine sorbents are critically reviewed.These include severa PEI or TEPA impregnated adsorbents and APTES-grafted systems.