Pdf reaction path of ethanol and acetic acid steam. Hydrogenproductionbyethanolsteamreformingonnisio2 catalysts. Steam reacts with natural gas, producing hydrogen and carbon monoxide. Hydrogen production by the steam reforming of bioethanol. Insight into steam reforming of ethanol to produce hydrogen. At present, most of the worlds hydrogen is produced from natural gas 97 % ch 4 by a process called steam reforming 38. Gas phase byproducts of catalytic ethanol reforming were analyzed for temperaturedependent trends and al reaction kinetic parameters. Bio ethanol is a renewable energy carrier and its use in the reforming of bio ethanol is promising for hydrogen production. Hydrogen is a promising fuel for fuel cells and can be produced by steam reforming of natural gas, methanol and gasoline. Pdf steam reforming of ethanol on rhsiceo 2 washcoated.
Steam reforming is a high temperature endothermic process which uses a catalyst to react the glycerol with water to produce hydrogen. Five nial catalysts modified with ca, ce, mg, mn and zn were investigated using a fixedbed reactor. Production of hydrogen by steamreforming of ethanol has been performed using different catalytic systems. 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. The steam reforming of bioethanol esr acetaldehyde which is transformed by a decarbonylation reaction to ch4.
The effect of operating conditions such as the temperature, space time, watertoethanol molar ratio, and oxygentoethanol molar ratio on the product distribution is evaluated. Advances in ethanol reforming for the production of hydrogen. A nonsyngas direct steam reforming route is investigated for the conversion of methanol to hydrogen and carbon dioxide over a cuzngaox catalyst. Influence of calcination temperature on supports zahira yaakob 1, ahmed bshish 1, ali ebshish 1, siti masrinda tasirin 1 and fatah h. Steam reforming or steam methane reforming is a method for producing syngas hydrogen and carbon monoxide by reaction of hydrocarbons with water.
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. 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 reaction tests were made under differential reactor conditions. Catalytic steam reforming of methanol to produce hydrogen. 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. 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. Preparation of hydrogen from glycerol via steam reforming. Mechanistic kinetic models for steam reforming of concentrated crude. Kinetics, catalysis and mechanism of methane steam reforming. Hydrogen production from steam reforming of ethanol. Steam methane reforming is the most common and economical way to make hydrogen.
Analysis of ethanol reforming system configurations. Optimal design, modeling and simulation of an ethanol steam reforming reactor. 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. Parametric study of hydrogen production from ethanol steam. Mechanistic aspects of the ethanol steam reforming. High pressure ethanol reforming for distributed hydrogen. Cfd simulation of ethanol steam reforming system for. Water enters the furnace, producing steam at a very high temperature. The primary ways in which methane, is converted to hydrogen involve reaction with either steam. Nisio2 catalysts are active for h2 production by ethanol steam reforming over 400.
Stable catalyst performance article pdf available in international journal of hydrogen energy 431 december 2017 with. Pdf new catalysts for hydrogen production by steam reforming of bioethanol have been developed. 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. Implementing glycerol steam reforming will make hydrogen production less dependent on finite fossil fuels 32. Its production is simple and cheap and hence steam reforming of ethanol to produce hydrogen for fuel cells is attractive. Steamethanol ratio ghsv ethanol conversion temperature catalyst exit gas composition. 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. 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. Steam reforming of ethanol on rhsiceo 2 washcoated monolith catalyst.
Production of synthesis gases from ethanol steam reforming. Steam reforming of ethanol for hydrogen production. A constant mixture of n 2 and h 2och 3choh 4 molar ratio was supplied to the reactor at 92c. Hydrogen production by bioethanol reforming for small. In the water shift reactor, carbon monoxide and steam react to form carbon dioxide and more hydrogen gas. The most effective was the oxide zno with redox characteristics, on which the yield of hydrogen.
Smallscale steam reforming units are currently subject to scientific research. Modification of nonnoble catalysts using an appropriate approach to minimize the. Chemical looping steam reforming clsr is a novel hydrogen production. Methanol steam reforming for fuel cell applications. Bioethanol steam reforming on nial2o3 catalyst request pdf. The best catalyst among the prepared solids was 5cuco6al2 as it showed a complete ethanol conversion and the highest hydrogen and carbon dioxide. Hydrogen production by catalytic ethanol steam reforming. Pdf catalysts for h2 production using the ethanol steam reforming. Insight into steam reforming of ethanol to produce.
Methane is an inevitable byproduct of reforming processes. Controllability study of an ethanol steam reforming. Chemical reaction the overall reaction of hydrogen production by steam reforming of glycerol is as follows. The ni and co metals peaks at ht merged into one reduction peak, indicating that.
Highly stable catalysts for ethanol steam reforming. 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. Steam reforming is the most efficient and popular way of producing hydrogen gas. Catalytic steam reforming of methanol to produce hydrogen on. The steam reforming of ethanol was carried out in a glass fixedbed flow reactor at atmospheric pressure. The best catalyst among the prepared solids was 5cuco6al2 as it showed a complete ethanol conversion and the highest.
Steam reforming of ethanol for hydrogen production over cuco. Mechanistic aspects of the steam reforming of ethanol reaction. Steam reforming of ethanol for hydrogen production over cu. Hydrogen production by bioethanol reforming for smallscale. This years work also involved preliminary studies with different feedstocks such as dimethylether dme. Steam reforming of liquid hydrocarbons is seen as a potential way to provide fuel for fuel cells.
The performances of nibased catalysts for ethanol steam reforming in a low temperature range. A thermodynamic analysis of ethanol co 2 reforming process is done using gibbs free energy minimization methodology. The reaction temperature was increased from 500 to 650c and the products. Pdf hydrogen production by steam reforming of ethanol. The catalyst plays a crucial role for the production of hydrogen through ethanol reforming. This might mitigate the distribution problems associated with hydrogen. The decomposition of methanol leads to a product gas containing up to 67% hydrogen and 33% carbon monoxide. Catalytic activity of skeletal nickel catalyst for low. Figure 3 shows the effect of change in pressure, ccer, and temperatures on ch 4 formation in the dry reforming of ethanol.
Ethanol steam reforming esr is an endothermic process with the following. 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. The reaction pathway proposed for ethanol steam reforming catalyzed by nial 2 o 3 was based on the work of haryanto et al. Many thanks to all the members of our steam reforming and fuel cells group for all the helpful weekly discussions.
Higher activity of water gas shift reaction and methanation contributes. The steam reforming of ethanol has been widely investigated over several catalytic materials. The test reaction was ethanol steam reforming carried out at a temperature interval of 250c750c and a ratio h2oc2h5oh of 31. Hydrogen production by steam reforming of ethanol over nickel catalysts supported on sol gel made alumina. 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.
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. 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. The mechanism of steam reforming of higher hydrocarbons is more complex. Hydrogen production from catalytic reforming of the. Hydrogen production from chemical looping steam reforming of. 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. Article pdf available in international journal of chemical reactor. H 2 ch 4 co co 2 ethylene ethane precious metal nonprecious metal etoh consumption rate 1 2 coexp rt e c a. The main purpose of this technology is hydrogen production. One of the most interesting routes to produce energy from biomass is the production of hydrogen by bio ethanol steam reforming. Process engineering aspects of ethanol steam reforming are discussed here. In addition, promising new technologies such as membrane reactors and electrochemical reforming for.
Deactivation, related to carbonaceous compounds deposition, is considered the principal inconvenience of the catalytic. The catalytic steam reforming of ethanol is a promising route for the sustainable production of hydrogen for use in fuel cells. The reaction is strongly endothermic consumes heat. Highly stable catalysts for ethanol steam reforming ayman m. In this work, a set of materials containing mixtures of co3o4ceo2 5. Ethanol can be prepared from agricultural residues and hence is a renewable resource.
Changing the oxygen mobility in coceria catalysts by ca. 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. Production of hydrogen by steam reforming of ethanol has been performed using different catalytic systems. Highpressure steam reforming of ethanol free download as powerpoint presentation. Hydrogen production by steam reforming of ethanol over. Niceo2zro2 catalysts were prepared via coprecipitation and characterized by n2 adsorptiondesorption, xrd, sem, and tpr techniques. Reaction network and kinetic analysis of ethanol steam. Pdf steam reforming of ethanol for hydrogen production. 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.
Hydrogen production by ethanol steam reforming over co. An investigation on reaction scheme and kinetics for ethanol steam reforming on skeletal nickel catalysts is described. 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. 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. Steam reforming of methanol for fuel cell grade hydrogen. Merge of methane reformer into this article as per. 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. Low temperature catalytic ethanol conversion over ceria.
Origin and nature of coke in ethanol steam reforming and its role. Ethanol steam reforming, a potential technology of hydrogen production for fuel cell application, has attracted great research attention recently. 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. The watergas shift reaction is examined in the reforming process. Bioethanol is a renewable energy carrier and its use in the reforming of bioethanol is promising for hydrogen production. The most simple conversion method, as only methanol is used in the feeding, is thermal or catalytic decomposition eq. Controllability study of an ethanol steam reforming process. Hydrocarbon reforming three primary techniques can be applied to produce hydrogen from hydrocarbons.
In last two decades research interest in the area of catalytic steam reforming of ethanol has been increased. Results of catalytic chemic data indicate that catalyst composition plays a significant role in lowtemperature ethanol conversion. Nonsyngas direct steam reforming of methanol to hydrogen. Steam reforming of ethane and ethanol over rhalumina. Hydrogen production from steam reforming of ethanol over an ir. 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 reaction is very endothermic and typically occurs in a fixed bed reactor, heated by an open flame furnace with natural gas as the feedstock. 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.
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. Analysis of byproduct s demonstrate how ethanol steam reforming over yield. The steam methane reforming process can be broken down into five distinct steps. Catalytic steam reforming of ethanol sre is a promising route for the production of renewable hydrogen h 2. A powerfunction rate expression was obtained with reaction orders of 1. Stable hydrogen production from ethanol through steam. Highpressure steam reforming of ethanol ethanol hydrogen.
322 902 1239 122 639 1031 660 1063 566 1136 1346 658 1450 1145 535 611 1234 911 615 1261 126 63 1280 517 167 668 1216 508 1341 969 1066 871 688 476 1002 502 523