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Energies 2019, 12, x FOR PEER REVIEW 5 of 15 Energies 2019, 12, 469 5 of 15 Figure2.InfluenceofCO additionontheCOconversionandcomparisonofexperimentaldataand Figure 2. Influence of CO2 ad2dition on the CO conversion and comparison of experimental data and kinetic model, Equations (4) and (6). The CO conversion is also indicated for experiments with CO kinetic model, Equations (4) and (6). The CO2 co2nversion is also indicated for experiments with CO2 2 addition(1.13vol%CO,10%H O,55%H ,0–18%CO ,restN ,m =2g,p=1bar,τ(190◦C)= addition (1.13 vol% CO, 10% H2O, 525% H2, 0‒182 % CO2, rest 2N2, mcat =22 g,capt = 1 bar, τ(190 °C) = 260 kg 2−360 kg s·m−3). The equation describing the CO s·m ). The equation describing the CO2 methanation, which was used here to calculate the CO2 2 CO2 conversion is introduced in Section 3.2. methanation, which was used here to calculate the conversion is introduced in Section 3.2. Table 2. Parameters of the kinetics of CO methanation (see Equations (4) and (5)). Table 2. Parameters of the kinetics of CO methanation (see Equations (4) and (5)). ΕΑ,CO k0,CO K1 K2 3.2.3K.2i.nKetiincestoicfsCoOfC2 MOetMhaenthatainoantion 2 Value −1 90 kJ·mol Parameter Parameter EA,CO Value k 3.61 × 10 3.61 × 107 m6·s−1·kg−1·mol−1 3 3 −1 −1 23 m23·mo·lmol 0.3 m3·m−1ol−1 0.3 m ·mol K1 K 2 2222 dC CO22 CO − =CrO= 2 CO,2 90 kJ·mol−1 7 0,CO m6 ·s− 1 ·kg− 1 ·mol− 1 COC2Oisailsoalssuobsjeucbtjetoctmtoetmhaenthaatinoant,ioanlt,haoltuhgohutgohatoloawleorweexrtenxtecnotmcopmarpedarteodCtoOC.SOo.,Stoh,etrhearcetiaocntion 2 of CoOf C2 wOithwHith2 wHaswalassoasltsuodsiteudd,iaetdf,irasttfiwrsithwouitthCouOtiCnOthienfteheed.feTehde.reTbhye,rCebOy,wCaOs nwoatsdneotetcdtedtefcoterdTfor 22 andanthdethqeueqsutieosntiownhwethetrhCerOC2Ois2diisredcitrleyctcloyncvoenrvtedrtteodmtoetmhaetnheaonrevoiravRiaWRGWSGaSndansdubssuebqsueeqnuteCntOCO memtheatnhaatnioantioisndisisdcuiscsuesdseinddinetdaeiltainiliSnecSteiocntio3n.33..F3.orFoCrOC2Omemtheatnhatnioanti,oan,LanLgamngumiru–Hir–inHsihneslhweolwodood 2 apparpoparcohawchawsalsoalusoseudsetodftiottfihtethexepeexrpimereimnteanltdaaltdaa:ta: dCCO kCO (T)cCO cH ◦◦ <2T00<°C20,0anCd,eavnednefvoernTfo>r2T00>°2C00theCctohnetecnonttwenatswleassltehsasnth2a5np2p5mp.pTmh.eTphoesspiobslesibrolelerolfetohfetRheWRGWSGS k (T)c c 22H (6) −=r= ,(6) dτCO dτ 1+K(T)c +K(T)c +Kc 23 4CO5HO 2 1+2K(T)c +K(T)c +Kc CO 3 CO2 4 2 CO 5 H2O ci (i = CO, CO2, H2, H2O) is the gas concentration, τ is the residence time defined as the ratio of catalyst ci (i = CO, CO2, H2, H2O) is the gas concentration, τ is the residence time defined as the ratio of catalyst mass to the volume flow at reactor temperature and atmospheric pressure, K3(T), K4(T) and K5 are the mass to the volume flow at reactor temperature and atmospheric pressure, K3(T), K4(T) and K5 are adsorption constants for CO2, CO and H2O, respectively, and ki(T) is the reaction rate constant the adsorption constants for CO2, CO and H2O, respectively, and ki(T) is the reaction rate constant according to the Arrhenius law (Equation (5)). The influence of temperature on the adsorptions Ki is according to the Arrhenius law (Equation (5)). The influence of temperature on the adsorptions Ki is given by: given by: KiT= K0,i e R T −∆Hi (7) Ki(T)= K0,i e R T (7) CO, CO2, and H2O have an influence on the reaction rate of CO2, but the CO concentration has the highest impact. For instance, at 190 °C, the adsorption constant for CO (K4) is 14.6 m3·mol−1, and CO, CO2, and H2O have an influence on the reaction rate of CO2, but the CO concentration has the ◦ 3 −1 33−1−1 thus much higher than the value for CO2 (K3) with 0.17 m ·mol or for H2O (K5) with 1.1 m ·mol . The highest impact. For instance, at 190 C, the adsorption constant for CO (K4) is 14.6 m ·mol , and thus 3 −1 3 −1 adsorption constant for H2O turned out to be independent of temperature. Most probably, the active much higher than the value for CO2 (K3) with 0.17 m ·mol or for H2O (K5) with 1.1 m ·mol . catalyst surface (Ru) is blocked by adsorbed CO due to strong adsorption of CO compared to CO2 The adsorption constant for H2O turned out to be independent of temperature. Most probably,PDF Image | Selective Methanation of CO over a Ru-y-AI2O3 Catalyst in CO2 H2
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