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1.
CO2 methanation over supported ruthenium catalysts is considered to be a promising process for carbon capture and utilization and power-to-gas technologies. In this work 4% Ru/Al2O3 catalyst was synthesized by impregnation of the support with an aqueous solution of Ru(OH)Cl3, followed by liquid phase reduction using NaBH4 and gas phase activation using the stoichiometric mixture of CO2 and H2 (1:4). Kinetics of CO2 methanation reaction over the Ru/Al2O3 catalyst was studied in a perfectly mixed reactor at temperatures from 200 to 300 °C. The results showed that dependence of the specific activity of the catalyst on temperature followed the Arrhenius law. CO2 conversion to methane was shown to depend on temperature, water vapor pressure and CO2:H2 ratio in the gas mixture. The Ru/Al2O3 catalyst was later tested together with the K2CO3/Al2O3 composite sorbent in the novel direct air capture/methanation process, which combined in one reactor consecutive steps of CO2 adsorption from the air at room temperature and CO2 desorption/methanation in H2 flow at 300 or 350 °C. It was demonstrated that the amount of desorbed CO2 was practically the same for both temperatures used, while the total conversion of carbon dioxide to methane was 94.2–94.6% at 300 °C and 96.1–96.5% at 350 °C.  相似文献   

2.
We prepared various Ru catalysts supported on different supports such as yttria-stabilized zirconia (YSZ), ZrO2, TiO2, SiO2 and γ-Al2O3 with a wet impregnation method. We applied them to the selective CO removal in a hydrogen-rich stream via the preferential CO oxidation (PROX) and the selective CO methanation simultaneously. Among them, Ru/YSZ showed the highest CO conversion especially at low temperatures. Several measurements: the N2 physisorption, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), the CO chemisorptions, the temperature-programmed oxidation (TPO), the temperature-programmed reduction (TPR), the temperature-programmed desorption (TPD) of CO2 with mass spectroscopy and the transmission electron microscopy (TEM), were conducted to characterize the catalysts. No linear correlation can be found between the amount of CO chemisorbed at 300 K and the PROX activity. On the other hand, the facile activation of O2 appeared to be closely related to the high PROX activity, judging by the TPO experiment. In addition, the strong adsorption of CO2 suppressed the low-temperature PROX activity. Ru/YSZ can be easily oxidized and also reduced at low temperatures. It is found that Ru/YSZ uptakes only small amounts of CO2, which can be desorbed at low temperatures. Ru/YSZ can reduce the high inlet CO concentration to be less than 10 ppm even in the presence of H2O and CO2.  相似文献   

3.
The catalytic behavior of Ni/Ce-ZrO2/θ-Al2O3 has been investigated in the partial oxidation of methane (POM) toward synthesis gas. The catalyst showed high activity and selectivity due to the heat treatment of the support and the promotional effect of Ce-ZrO2. It is suggested that the support was stabilized through the heat treatment of γ-Al2O3 and the precoating of Ce-ZrO2, on which a protective layer was formed. Moreover, sintering of the catalyst was greatly suppressed for 24 h test. Pulse experiments of CH4, O2 and/or CH4/O2 with a molar ratio of 2 were systematically performed over fresh, partially reduced and well reduced catalyst. Results indicate that CH4 can be partially oxidized to CO and H2 by the reactive oxygen in complex NiOx species existing over the fresh catalyst. It is demonstrated that POM over Ni/Ce-ZrO2/θ-Al2O3 follows the pyrolysis mechanism, and both the carbonaceous materials from CH4 decomposition over metallic nickel and the reactive oxygen species present on NiOx and Ce-ZrO2 are intermediates for POM.  相似文献   

4.
CO impedes the low temperature (<170 °C) oxidation of C3H6 on supported Pt. Supported Au catalysts are very effective in the removal of CO by oxidation, although it has little propene oxidation activity under these conditions. Addition of Au/TiO2 to Pt/Al2O3 either as a physical mixture or as a pre-catalyst removes the CO and lowers the light-off temperature (T 50) for C3H6 oxidation compared with Pt catalyst alone by ~54 °C in a feed of 1% CO, 400 ppm C3H6, 14% O2, 2% H2O.  相似文献   

5.
The concept of “waste-to-wealth” is spreading awareness to prevent global warming and recycle the restrictive resources. To contribute towards sustainable development, hydrogen energy is obtained from syngas (CO and H2) generated from waste gasification, followed by CO oxidation and CO2 removal. In H2 generation, it is key to produce more purified H2 from syngas using heterogeneous catalysts. In this respect, we prepared Pt/Al2O3 catalyst with nanoporous structure using precipitation method, and compared its catalytic activity with commercial alumina (Degussa). Based on the results of XRD and TEM, it was found that metal particles did not aggregate on the alumina surface and showed high dispersion. Optimum condition for CO conversion was 1.5 wt% Pt loaded on Al2O3 support, and pure hydrogen was obtained after removal of CO2 gas.  相似文献   

6.
CuCl2-SCR catalysts prepared by an improved impregnation method were studied to evaluate the catalytic performance for gaseous elemental mercury (Hg0) oxidation in simulated flue gas. Hg0 oxidation activity of commercial SCR catalyst was significantly improved by the introduction of CuCl2. Nitrogen adsorption, XRD, XRF and XPS were used to characterize the catalysts. The results indicated that CuCl2 was well loaded and highly dispersed on the catalyst surface, and that CuCl2 played an important role for Hg0 catalytic oxidation. The effects of individual flue gas components on Hg0 oxidation were also investigated over CuCl2-SCR catalyst at 350 oC. The co-presence of NO and NH3 remarkably inhibited Hg0 oxidation, while this inhibiting effect was gradually scavenged with the decrease of GHSV. Further study revealed the possibility of simultaneous removal of Hg0 and NO over CuCl2-SCR catalyst in simulated flue gas. The mechanism of Hg0 oxidation was also investigated.  相似文献   

7.
The production of isophthalic acid (IPA) from the oxidation of m-xylene (MX) by air is catalyzed by H3PW12O40 (HPW) loaded on carbon and cobalt. We used H2O2 solution to oxidize the carbon to improve the catalytic activity of HPW@C catalyst. Experiments reveal that the best carbon sample is obtained by calcining the carbon at 700 °C for 4 h after being impregnated in the 3.75% H2O2 solution at 40 °C for 7 h. The surface characterization displays that the H2O2 modification leads to an increase in the acidic groups and a reduction in the basic groups on the carbon surface. The catalytic capability of the HPW@C catalyst depends on its surface chemical characteristics and physical property. The acidic groups play a more important part than the physical property. The MX conversion after 180 min reaction acquired by the HPW@C catalysts prepared from the activated carbon modified in the best condition is 3.81% over that obtained by the HPW@C catalysts prepared from the original carbon. The IPA produced by the former is 46.2% over that produced by the latter.  相似文献   

8.
The catalytic properties of Ni/Al2O3 composites supported on ceramic cordierite honeycomb monoliths in oxidative methane reforming are reported. The prereduced catalyst has been tested in a flow reactor using reaction mixtures of the following compositions: in methane oxidation, 2–6% CH4, 2–9% O2, Ar; in carbon dioxide and oxidative carbon dioxide reforming of methane, 2–6% CH4, 6–12% CO2, and 0–4% O2, and Ar. Physicochemical studies include the monitoring of the formation and oxidation of carbon, the strength of the Ni-O bond, and the phase composition of the catalyst. The structured Ni-Al2O3 catalysts are much more productive in the carbon dioxide reforming of methane than conventional granular catalysts. The catalysts performance is made more stable by regulating the acid-base properties of their surface via the introduction of alkali metal (Na, K) oxides to retard the coking of the surface. Rare-earth metal oxides with a low redox potential (La2O3, CeO2) enhance the activity and stability of Ni-Al2O3/cordierite catalysts in the deep and partial oxidation and carbon dioxide reforming of methane. The carbon dioxide reforming of methane on the (NiO + La2O3 + Al2O3)/cordierite catalyst can be intensified by adding oxygen to the gas feed. This reduces the temperature necessary to reach a high methane conversion and does not exert any significant effect on the selectivity with respect to H2.  相似文献   

9.
Compact natural gas reforming process using high-performance and long-lived CO preferential oxidation (PROX) over an activated Ru/Al2O3 catalyst has been developed for residential polymer electrolyte fuel cell (PEFC) systems. The long-term durability of the catalyst was demonstrated for more than 40,000 h. After 40,000 h operation, CO was removed from a reformed gas to below 1 ppm on the activated Ru/Al2O3 catalyst at [O2]/[CO] = 1.5. The high activity and selectivity of the catalyst were maintained for more than 40,000 h. Moreover, the start–stop durability for more than 3,000 cycles of the activated Ru/Al2O3 catalyst was also demonstrated without N2 purge.  相似文献   

10.
Kinetic models of CO hydrogenation to paraffinic hydrocarbons through Fischer-Tropsch synthesis (FTS) reaction were studied by using Langmuir-Hinshelwood Hougen-Watson (LHHW) model of 16 different reaction steps with a pseudo steady-state assumption (PSSA) on the prototype Pt-promoted Co/Al2O3 catalyst having a granule size of ~1 mm of spherical γ-Al2O3 support (surface area of 149m2/g). The derived kinetic models from ten sets of experimental data by altering the reaction conditions such as temperatures, pressures, space velocities and H2/CO molar ratios were found to be well fitted with reasonable kinetic parameters and small errors of conversion of CO and hydrocarbon distributions in terms of mean absolute relative residual (MARR) and relative standard deviation error (RSDE). The derived reaction rates and CO activation energy of -86 kJ/mol well correspond to the our previously reported results using power-type catalysts. Based on the LHHW model with PSSA, the possible chemical intermediates on the granule ball-type Co-Pt/Al2O3 surfaces were precisely considered to explain the typical adsorption, initiation, propagation and termination steps of FTS reaction as well as to derive elementary reaction rates with their kinetic parameters and hydrocarbon distributions. The derived kinetic models were further used to verify temperature-profiles in a pilot-scale fixed-bed tubular FTS reactor with a packing depth of 100 cm catalyst, and it confirmed that the temperature gradients were less than 10 °C in a length of reactor by effectively removing the generated heat by an exothermic FTS reaction.  相似文献   

11.
A series of Mn-promoted 15 wt-% Ni/Al2O3 catalysts were prepared by an incipient wetness impregnation method. The effect of the Mn content on the activity of the Ni/Al2O3 catalysts for CO2 methanation and the comethanation of CO and CO2 in a fixed-bed reactor was investigated. The catalysts were characterized by N2 physisorption, hydrogen temperature-programmed reduction and desorption, carbon dioxide temperature-programmed desorption, X-ray diffraction and highresolution transmission electron microscopy. The presence of Mn increased the number of CO2 adsorption sites and inhibited Ni particle agglomeration due to improved Ni dispersion and weakened interactions between the nickel species and the support. The Mn-promoted 15 wt-% Ni/Al2O3 catalysts had improved CO2 methanation activity especially at low temperatures (250 to 400 °C). The Mn content was varied from 0.86% to 2.54% and the best CO2 conversion was achieved with the 1.71Mn-Ni/Al2O3 catalyst. The co-methanation tests on the 1.71Mn-Ni/Al2O3 catalyst indicated that adding Mn markedly enhanced the CO2 methanation activity especially at low temperatures but it had little influence on the CO methanation performance. CO2 methanation was more sensitive to the reaction temperature and the space velocity than the CO methanation in the co-methanation process.
  相似文献   

12.
The effects of ZrO2 content on the CO oxidation activity in a series of CuOx/CexZr1−xO2 (x = 0, 0.15, 0.5, 0.7 and 1) catalysts were investigated, both in the absence and in the presence of H2, i.e. preferential CO oxidation—PROX. The investigation was performed under light-off conditions to focus the effects of transients and shut-down/start-up cycles on the performance; such phenomena are expected to affect the activity of PROX catalysts in small/delocalised fuel reformers. Evidence has been obtained for a transition from an “oxidized” towards a “reduced” state of the catalyst under the simulated PROX reaction conditions as a function of the reaction temperature, leading to different active species under the reaction conditions. Both CO oxidation activity and PROX selectivity appear to be affected by this process. IR characterisation of the surface copper species suggests an important role of reduced cerium sites in close contact with copper clusters on the CO oxidation activity at low temperatures.  相似文献   

13.
Methanol steam reforming (MSR) and preferential CO oxidation (PROX) were studied with the view of improving the generation of H2-rich gases. In MSR, conventional catalysts of methanol synthesis were tested, various Cu-based catalysts were prepared and studied. A theoretic kinetic model (based on the reaction mechanism established using independent methods [1]) is developed and checked out. PROX was studied over various Ru/Al2O3 catalysts using a flow “quasi-adiabatic” reactor. On-line recording of gas temperature in the catalyst bed and CO residual concentration at varied reaction conditions allowed to observe ignition and extinction of the catalyst surface and the transition states of the process. It is shown that in the ignition mode a sharp decrease in CO residual concentration can be achieved. The combination of proposed catalyst and the control of the macrokinetic regime of PROX allows high degree of CO removal from gaseous mixtures produced by MSR. Residual CO content in a H2-rich gaseous mixture can be lowered to < 15 ppm at GHSV∼100 m3/(kg cat)/h and O2/CO ratio of 1. Obtained data show the possibility of designing a high-throughput set-up for generation of H2-rich gases from methanol with one-step cleaning from the CO impurity.  相似文献   

14.
Spherical carbon (SC) with a diameter of ca. 9 μm was synthesized by a hydrothermal method using sucrose as a carbon precursor. The spherical carbon was then modified to have a positive charge, and thus, to provide a site for the immobilization of H5PMo10V2O40 (PMo10V2) catalyst. The PMo10V2 catalyst was immobilized on the surface-modified spherical carbon by taking advantage of the overall negative charge of [PMo10V2O40]5−. The PMo10V2 catalyst immobilized on the spherical carbon (PMo10V2/SC) was applied to the vapor-phase 2-propanol conversion reaction. In the catalytic reaction, the PMo10V2/SC catalyst showed a higher 2-propanol conversion than the unsupported PMo10V2 catalyst. Furthermore, the PMo10V2/SC catalyst showed enhanced oxidation catalytic activity (formation of acetone) and the suppressed acid catalytic activity (formation of propylene and isopropyl ether) compared to the unsupported PMo10V2 catalyst. The enhanced oxidation activity of PMo10V2/SC catalyst was due to the fine dispersion of [PMo10V2O40]5− on the spherical carbon formed via chemical immobilization.  相似文献   

15.
A K-promoted 10Ni-(x)K/MgAl2O4 catalyst was investigated for the combined H2O and CO2 reforming (CSCR) of coke oven gas (COG) for syngas production. The 10Ni-(x)K/MgAl2O4 catalyst was prepared by co-impregnation, and the K content was varied from 0 to 5 wt%. The BET, XRD, H2-chemisorption, H2-TPR, and CO2-TPD were performed for determining the physicochemical properties of prepared catalysts. Except under the condition of a K/Ni=0.1 (wt%/wt%), the Ni crystal size and dispersion decreased with increasing K/Ni. The coke resistance of the catalyst was investigated under conditions of CH4: CO2: H2: CO:N2=1 : 1 : 2 : 0.3 : 0.3, 800 °C, 5 atm. The coke formation on the used catalyst was examined by SEM and TG analysis. As compared to the 10Ni/MgAl2O4 catalyst, the Kpromoted catalyst exhibited superior activity and coke resistance, attributed to its strong interaction with Ni and support, and the improved CO2 adsorption characteristic. The 10Ni-1K/MgAl2O4 catalyst exhibited optimum activity and coke resistance with only 1wt% of K.  相似文献   

16.
The results of experimental studies of synthesis of the hollandite phase K2Ga2Ti6O16 using initial mixtures of different dispersion compositions obtained by two methods, i.e., mechanical dispersion (MD) (followed by solid-phase sintering) and sol-gel method (Pechini method, MP), are reported. The catalytic properties of the obtained materials in the reactions of carbon monoxide (CO) and hydrogen (H2) oxidation have been determined. It has been demonstrated that an increase in the catalytic activity in the CO oxidation reaction is observed on the samples obtained using the sol-gel method, in which the hollandite phase content is higher and crystallization is more complete. The samples obtained using the MD method are characterized by a low porosity and activity in comparison with those produced by the Pechini method.  相似文献   

17.
The electrochemical promotion of the CO2 hydrogenation reaction on porous Rh catalyst–electrodes deposited on Y2O3-stabilized-ZrO2 (or YSZ), an O2− conductor, was investigated under atmospheric total pressure and at temperatures 346–477 °C, combined with kinetic measurements in the temperature range 328–391 °C. Under these conditions CO2 was transformed to CH4 and CO. The CH4 formation rate increased by up to 2.7 times with increasing Rh catalyst potential (electrophobic behavior) while the CO formation rate was increased by up to 1.7 times with decreasing catalyst potential (electrophilic behavior). The observed rate changes were non-faradaic, exceeding the corresponding pumping rate of oxygen ions by up to approximately 210 and 125 times for the CH4 and CO formation reactions, respectively. The observed electrochemical promotion behavior is attributed to the induced, with increasing catalyst potential, preferential formation on the Rh surface of electron donor hydrogenated carbonylic species leading to formation of CH4 and to the decreasing coverage of more electron acceptor carbonylic species resulting in CO formation.  相似文献   

18.
A co-precipitation method was employed to prepare Ni/Al2O3-ZrO2, Co/Al2 O3-ZrO2 and Ni-Co/Al2O3-ZrO2 catalysts. Their properties were characterized by N2 adsorption (BET), thermogravimetric analysis (TGA), temperature-programmed reduction (TPR), temperature-programmed desorption (CO2-TPD), and temperature-programmed surface reaction (CH4-TPSR and CO2-TPSR). Ni-Co/Al2O3-ZrO2 bimetallic catalyst has good performance in the reduction of active components Ni, Co and CO2 adsorption. Compared with mono-metallic catalyst, bimetallic catalyst could provide more active sites and CO2 adsorption sites (C + CO2 = 2CO) for the methane-reforming reaction, and a more appropriate force formed between active components and composite support (SMSI) for the catalytic reaction. According to the CH4-CO2-TPSR, there were 80.9% and 81.5% higher CH4 and CO2 conversion over Ni-Co/Al2O3-ZrO2 catalyst, and its better resistance to carbon deposition, less than 0.5% of coke after 4 h reaction, was found by TGA. The high activity and excellent anti-coking of the Ni-Co/Al2O3-ZrO2 catalyst were closely related to the synergy between Ni and Co active metal, the strong metal-support interaction and the use of composite support.  相似文献   

19.
Herein, we studied the influence of calcination temperature (500–800 °C) of Ni/CeO2 and Ni/Ce0.8Zr0.2O2 catalysts on the specific surface area, pore volume, crystalline size, lattice parameter, chemical bonding and oxidation states, nickel dispersion and CH4/CO production rate in CO2 methanation. In general, the catalytic performance revealed that Zr doping catalysts could increase the CH4 production rate. Combined with the production rate and the characterizations results, we found that the combination of nickel dispersion, peak area of CO2–TPD and OII/(OII + OI)) play the critical role in increasing the CH4 production rate. It is well to be mentioned that the CO production rate is strongly influenced by the nickel dispersion. Furthermore, the in-situ DRIFTS confirmed that the CO originates from the decomposition of H-assisted formate species.  相似文献   

20.
Properties of Pt0.5M0.5 nanopowders (M = Fe, Co, Ni) of alloys obtained via the decomposition of double complex salts [Pt(NH3)5Cl][Fe(C2O4)3] ? 4H2O, [Pt(NH3)4][Co(C2O4)2(H2O)2] ? 2H2O, and [Pt(NH3)4][Ni(C2O4)2(H2O)2] ? 2H2O, respectively, are studied in the reaction of preferential CO oxidation. It is shown that bimetallic Pt0.5M0.5 catalysts (M = Fe, Co, Ni) are much more active in the low temperature range than Pt nanopowder. The activity of the catalysts decreases in the order Pt0.5M0.5 ≥ Pt0.5M0.5 > Pt0.5M0.5 @ Pt. The higher activity of bimetallic Pt0.5M0.5 catalysts in the reaction of preferential CO oxidation in the low-temperature range under conditions of dense Pt surface coverage by adsorbed CO molecules is most likely caused by the activation of CO on Pt atoms, the activation of O2 on atoms of the second metal (Fe, Co, Ni), and the reaction that occurs at the sites of contact between the atoms of platinum and the atoms of the second metal on the surfaces of the alloy’s nanoparticles. The bimetallic systems investigated in this work can be used to improve catalysts of practically important preferential CO oxidation reaction. These systems have considerable potential in the afterburning reactions of CO and hydrocarbons; hydrogenation reactions; electrochemical reactions; and many others. The means used in the preparation of bimetallic nanopowders based on the decomposition of double complex salts is simple, does not require the use of expensive or complex reagents, and can be easily adapted to produce supported catalysts containing Pt0.5M0.5 metal alloys (M = Fe, Co, Ni).  相似文献   

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