Steam reforming of ethanol for hydrogen production over cu. An investigation on reaction scheme and kinetics for ethanol steam reforming on skeletal nickel catalysts is described. Muhammad bilal 1, claire gillan, sam french2, martin fowles2 and s david jackson1 1centre for catalysis research, westchem, university of glasgow, glasgow g12 8qq, scotland, uk 2johnson matthey plc, belasis ave, billingham ts23 1lb uk. The effect of operating conditions such as the temperature, space time, watertoethanol molar ratio, and oxygentoethanol molar ratio on the product distribution is evaluated. Analysis of byproduct s demonstrate how ethanol steam reforming over yield. The reaction is very endothermic and typically occurs in a fixed bed reactor, heated by an open flame furnace with natural gas as the feedstock.
Kinetics, catalysis and mechanism of methane steam reforming. The bioethanol steam reforming over nickelbased catalysts when the temperature is within the range of 700 to 800 k is studied for fuel cell applications. Pdf catalysts for h2 production using the ethanol steam reforming. Steam reforming is a high temperature endothermic process which uses a catalyst to react the glycerol with water to produce hydrogen. Catalytic steam reforming of methanol to produce hydrogen.
The primary ways in which methane, is converted to hydrogen involve reaction with either steam. Hydrogen production by catalytic ethanol steam reforming. H 2 ch 4 co co 2 ethylene ethane precious metal nonprecious metal etoh consumption rate 1 2 coexp rt e c a. Analysis of ethanol reforming system configurations. In this sense, steam reforming of bioethanol is a very interesting alternative among the various processes proposed for hydrogen production, because ethanol is abundantly available from biomass, is easy to store and nontoxic 2, 3. Reaction network and kinetic analysis of ethanol steam. Parametric study of hydrogen production from ethanol steam. In this regard, the oxidative steam reforming of ethanol on nonnoble catalyst is a good approach for hydrogen production though the carbonaceous deposition is comparatively lower than esr, but the overall yield of hydrogen per mole of ethanol is also lower. The steam methane reforming process can be broken down into five distinct steps. Highly stable catalysts for ethanol steam reforming. Stable hydrogen production from ethanol through steam. Article pdf available in international journal of chemical reactor. At present, most of the worlds hydrogen is produced from natural gas 97 % ch 4 by a process called steam reforming 38. Methanol steam reforming for fuel cell applications.
Hydrogen is a promising fuel for fuel cells and can be produced by steam reforming of natural gas, methanol and gasoline. The test reaction was ethanol steam reforming carried out at a temperature interval of 250c750c and a ratio h2oc2h5oh of 31. Pdf steam reforming of ethanol for hydrogen production. Pdf reaction path of ethanol and acetic acid steam. Influence of calcination temperature on supports zahira yaakob 1, ahmed bshish 1, ali ebshish 1, siti masrinda tasirin 1 and fatah h. Merge of methane reformer into this article as per. Hydrogen production by bioethanol reforming for small. Steam reforming is the most studied and used in industry since it has the highest hydrogen yield 47, and a h 2co ratio of about 31 would be produced. A thermodynamic analysis of ethanol co 2 reforming process is done using gibbs free energy minimization methodology. Methane is an inevitable byproduct of reforming processes.
A constant mixture of n 2 and h 2och 3choh 4 molar ratio was supplied to the reactor at 92c. The reaction pathway proposed for ethanol steam reforming catalyzed by nial 2 o 3 was based on the work of haryanto et al. Water enters the furnace, producing steam at a very high temperature. The effect of operating conditions such as the temperature, space time, waterto ethanol molar ratio, and oxygento ethanol molar ratio on the product distribution is evaluated. Implementing glycerol steam reforming will make hydrogen production less dependent on finite fossil fuels 32. Therdthianwong a et al6 are the early group who worked on the ethanol steam reforming over nial 2 o 3 catalyst in a fixed bed reactor by studying the influence of temperature, steam to carbon ratio and feed rate of dilute ethanol solution on steam reforming reaction. The ni and co metals peaks at ht merged into one reduction peak, indicating that. The effect of calcium doping on the performance of coceo2 catalysts in ethanol steam reforming was examined using various characterization techniques including co temperatureprogrammed reduction, o2 and co pulse chemisorption, laser raman spectroscopy, xray diffraction, isotopically labeled oxygen exchange, and diffuse reflectance infrared fourier transform spectroscopy. For this process, the catalyst must be stable, active, selective, and maximize hydrogen production while minimizing the generation of byproducts, such as co and ch 4. The performances of nibased catalysts for ethanol steam reforming in a low temperature range. Highly stable catalysts for ethanol steam reforming ayman m. Strohm, vanessa lebarbier, guosheng li, david king and yong wang pacific northwest national laboratory, richland wa 99354 introduction in an effort to reduce pollutants and green house gas emissions, hydrogen is seen as a promising energy carrier.
The reaction tests were made under differential reactor conditions. Insight into steam reforming of ethanol to produce. Controllability study of an ethanol steam reforming process. Steam reforming of ethanol for hydrogen production over cuco. Hydrogen production by bioethanol reforming for smallscale. The decomposition of methanol leads to a product gas containing up to 67% hydrogen and 33% carbon monoxide. Many thanks to all the members of our steam reforming and fuel cells group for all the helpful weekly discussions.
Steam reacts with natural gas, producing hydrogen and carbon monoxide. Gas phase byproducts of catalytic ethanol reforming were analyzed for temperaturedependent trends and al reaction kinetic parameters. In addition, promising new technologies such as membrane reactors and electrochemical reforming for. Stable catalyst performance article pdf available in international journal of hydrogen energy 431 december 2017 with. Hydrogen production by steam reforming of ethanol over nickel catalysts supported on sol gel made alumina. Ethanol steam reforming, a potential technology of hydrogen production for fuel cell application, has attracted great research attention recently. Highpressure steam reforming of ethanol free download as powerpoint presentation. Modification of nonnoble catalysts using an appropriate approach to minimize the. Optimal design, modeling and simulation of an ethanol steam reforming reactor. Deactivation, related to carbonaceous compounds deposition, is considered the principal inconvenience of the catalytic. Catalytic steam reforming of methanol to produce hydrogen on. The main purpose of this technology is hydrogen production.
Hydrocarbon reforming three primary techniques can be applied to produce hydrogen from hydrocarbons. Nisio2 catalysts are active for h2 production by ethanol steam reforming over 400. Pdf hydrogen production by steam reforming of ethanol. The bio ethanol steam reforming over nickelbased catalysts when the temperature is within the range of 700 to 800 k is studied for fuel cell applications. Hydrogenproductionbyethanolsteamreformingonnisio2 catalysts. A nonsyngas direct steam reforming route is investigated for the conversion of methanol to hydrogen and carbon dioxide over a cuzngaox catalyst. In this work, a set of materials containing mixtures of co3o4ceo2 5. Steamethanol ratio ghsv ethanol conversion temperature catalyst exit gas composition. The catalyst plays a crucial role for the production of hydrogen through ethanol reforming.
Process engineering aspects of ethanol steam reforming are discussed here. Bioethanol steam reforming on nial2o3 catalyst request pdf. Hydrogen production by the steam reforming of bioethanol. Production of hydrogen by steamreforming of ethanol has been performed using different catalytic systems. The activity of catalysts depends on several factors such as the nature of the active metal catalyst and the catalyst support, the precursor used, the method adopted for catalyst preparation, and the presence of. Steam reforming is the most efficient and popular way of producing hydrogen gas. One of the most interesting routes to produce energy from biomass is the production of hydrogen by bio ethanol steam reforming. The most effective was the oxide zno with redox characteristics, on which the yield of hydrogen. Mechanistic aspects of ethanol steam reforming on pt, ni, and ptni catalysts supported on gammaal2o3 are investigated from the analysis of adsorbed species and gas phase products formed on catalysts during temperatureprogrammed desorption of ethanol and during ethanol steam reforming reaction. Mechanistic aspects of the ethanol steam reforming. Ethanol steam reforming esr is an endothermic process with the following. Hydrogen production from steam reforming of ethanol over an ir. Hydrogen production from chemical looping steam reforming of. Mechanistic aspects of the steam reforming of ethanol reaction.
Bioethanol is a renewable energy carrier and its use in the reforming of bioethanol is promising for hydrogen production. Hydrogen production from steam reforming of ethanol. Because ethanol can be produced from biomass cheaply, using bioethanol with large excess of water as the direct feed of steam reforming is believed to be a promising technology to produce hydrogen. The mechanism of steam reforming of higher hydrocarbons is more complex. Steam reforming is most widely used to generate hydrogen not only with nonrenewable fossil fuels coal, natural gas, petroleum but also with renewable raw materials such as ethanol. The best catalyst among the prepared solids was 5cuco6al2 as it showed a complete ethanol conversion and the highest hydrogen and carbon dioxide. Low temperature catalytic ethanol conversion over ceria. The best catalyst among the prepared solids was 5cuco6al2 as it showed a complete ethanol conversion and the highest. The steam reforming of ethanol was carried out in a glass fixedbed flow reactor at atmospheric pressure. The steam reforming of bioethanol esr acetaldehyde which is transformed by a decarbonylation reaction to ch4.
In last two decades research interest in the area of catalytic steam reforming of ethanol has been increased. In the water shift reactor, carbon monoxide and steam react to form carbon dioxide and more hydrogen gas. The basic idea is that for example a methanol tank and a steam reforming unit would replace the bulky pressurized hydrogen tanks that would otherwise be necessary. Steamreforming of ethanol for hydrogen production polymeric ionic liquid as a background electrolyte modifier enhancing the separation of inorganic anions by capillary electrophoresis enantioselective extraction of terbutaline enantiomers with. Steam reforming of ethanol for hydrogen production. The function of the steam reforming of ethanol on 5% rhal 2o 3 catalyst in producing h 2 to feed a molten carbonate fuel cell was investigated by s. Nonsyngas direct steam reforming of methanol to hydrogen. The reaction is strongly endothermic consumes heat. Hydrogen production by steam reforming of ethanol over. Steam reforming or steam methane reforming is a method for producing syngas hydrogen and carbon monoxide by reaction of hydrocarbons with water. Higher activity of water gas shift reaction and methanation contributes. Steam reforming of ethanol studied on rhsiceo 2 coated ceramic monoliths catalyst was stable for 96 h under reaction at 1028 k and water ethanol ratio of 3. Pdf optimal design, modeling and simulation of an ethanol.
The article also neglects that current fuel cells cant utilize the reformed hydrogen because carbon monoxide is a. Its production is simple and cheap and hence steam reforming of ethanol to produce hydrogen for fuel cells is attractive. Smallscale steam reforming units are currently subject to scientific research. High pressure ethanol reforming for distributed hydrogen. The steam reforming of ethanol has been widely investigated over several catalytic materials. Chemical looping steam reforming clsr is a novel hydrogen production. Advances in ethanol reforming for the production of hydrogen. Mechanistic kinetic models were postulated for the catalytic steam reforming of concentrated crude ethanol on a nibased commercial catalyst at atmosphere pressure in the temperature range of 673863 k, and at different catalyst weight to the crude ethanol molar flow rate ratio in the range 0. The steam reforming of ethanol on a nibased ceo2supported catalyst was studied using in situ xray diffraction xrd, operando diffuse reflectance infrared fourier transform spectroscopy drifts, and mass spectroscopy ms with a focus on the structural characterization of the catalysts, chemical identification of the reaction pathway, and understanding of the interaction between ni and the. Insight into steam reforming of ethanol to produce hydrogen. In the reforming reaction, natural gas is mixed with steam, heated to over 1,500 degrees fahrenheit, and reacted with nickel catalyst to produce hydrogen h. Alfredo tanaka for his useful insights regarding carbon. Pdf new catalysts for hydrogen production by steam reforming of bioethanol have been developed. Optimized process conditions were obtained with a steam reforming temperature of 800.
Figure 3 shows the effect of change in pressure, ccer, and temperatures on ch 4 formation in the dry reforming of ethanol. Pdf steam reforming of ethanol on rhsiceo 2 washcoated. Steam reforming of ethane and ethanol over rhalumina. Steam reforming of liquid hydrocarbons is seen as a potential way to provide fuel for fuel cells. Steam reforming of methanol for fuel cell grade hydrogen. This might mitigate the distribution problems associated with hydrogen. Controllability study of an ethanol steam reforming. Niceo2zro2 catalysts were prepared via coprecipitation and characterized by n2 adsorptiondesorption, xrd, sem, and tpr techniques. Five nial catalysts modified with ca, ce, mg, mn and zn were investigated using a fixedbed reactor. Mechanistic kinetic models for steam reforming of concentrated crude.
Cfd simulation of ethanol steam reforming system for. This years work also involved preliminary studies with different feedstocks such as dimethylether dme. Production of synthesis gases from ethanol steam reforming. Ethanol can be prepared from agricultural residues and hence is a renewable resource. A powerfunction rate expression was obtained with reaction orders of 1.
Preparation of hydrogen from glycerol via steam reforming. The catalytic steam reforming of ethanol is a promising route for the sustainable production of hydrogen for use in fuel cells. Steam methane reforming is the most common and economical way to make hydrogen. Origin and nature of coke in ethanol steam reforming and its role. The watergas shift reaction is examined in the reforming process. Chemical reaction the overall reaction of hydrogen production by steam reforming of glycerol is as follows. Pdf production of hydrogen by steam reforming of ethanol. Hydrogen production by ethanol steam reforming over co. In this sense, steam reforming of bio ethanol is a very interesting alternative among the various processes proposed for hydrogen production, because ethanol is abundantly available from biomass, is easy to store and nontoxic 2, 3.
Production of hydrogen by steam reforming of ethanol has been performed using different catalytic systems. Bio ethanol is a renewable energy carrier and its use in the reforming of bio ethanol is promising for hydrogen production. Changing the oxygen mobility in coceria catalysts by ca. Steam reforming of ethanol on rhsiceo 2 washcoated monolith catalyst. Highpressure steam reforming of ethanol ethanol hydrogen. The effects of reaction temperature, carbonequivalent space velocity gc1hsv, and steamtocarbon ratio sc on the performance of the catalysts for ethanol steam reforming esr were investigated. Ethanol conversion and h2 yield considerably increase with temperature and ni loading. The most simple conversion method, as only methanol is used in the feeding, is thermal or catalytic decomposition eq.
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