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1.
CuO/ZnO/CeO2/ZrO2 nanoflowers catalyst was grown on an Al2O3 foam ceramic by a one-step hydrothermal process, while a naked Al2O3 foam ceramic and an Al2O3 foam ceramic grown with ZnO nanorods that directly impregnated into the catalyst precursor solution were also fabricated simultaneously. The morphology, composition, redox property and specific surface area of catalysts on the three ceramics were investigated in detail. The catalyst-loaded ceramics were used as catalyst supports in a microreactor to study the catalytic performance for methanol steam reforming. Results showed that the microreactor with Al2O3 support grown with nanoflowers catalyst achieved 99.8% methanol conversion rate, 0.16 mol/h H2 flow rate at 310 °C, and an inlet methanol flow rate of 0.048 mol/h. Moreover, the microreactor exhibited 92% methanol conversion rate after 30 h continuous reaction.  相似文献   

2.
The Rh/Ce0·75Zr0·25O2–δ-ƞ-Al2O3/FeCrAl structured catalytic blocks of length 10, 20, and 60 mm were prepared and tested in the reactions of steam and autothermal reforming of n-hexadecane. It was found in a series of experiments on hexadecane steam reforming with the catalyst heating solely through the reactor wall that the complete conversion of hexadecane at a furnace temperature below 750 °C was not achieved even at GHSV = 10,000 h−1. Under these conditions, the formation of carbon on the catalyst surface was observed. At the reactor wall temperature of 800 °C, the complete conversion of hexadecane was achieved even in the 10 mm long catalytic block (GHSV = 60,000 h−1), accompanied by the formation of various intermediate light hydrocarbons. To achieve complete conversion of these intermediate compounds (mainly 1-alkenes), it is necessary to carry out the steam reforming reaction at GHSV = 10,000 h−1. At hexadecane autothermal reforming, heat is supplied to the reaction zone by exothermic oxidation reaction, which makes this process more efficient. In experiments with the use of additional external heat supply through the reactor wall, complete conversion of hexadecane occurred at GHSV = 120,000 h−1. To convert all by-products (mainly 1-alkenes) and achieve a nearly thermodynamic equilibrium distribution of the main reaction products (H2, CO, CO2), the reaction should be carried out at GHSV = 20,000 h−1. Without external heat supply, hexadecane conversion decreased, while the content of light hydrocarbons in the reaction products increased. An increase in the inlet amount of oxygen helps to compensate the heat losses in the reactor and to increase the efficiency of hexadecane autothermal reforming. The performed experiments allow better understanding of the processes which occur during the steam and autothermal reforming of diesel.  相似文献   

3.
《Journal of power sources》2005,145(2):702-706
An integrated microchannel methanol processor was developed by assembling unit reactors, which were fabricated by stacking and bonding microchannel patterned stainless steel plates, including fuel vaporizer, heat exchanger, catalytic combustor and steam reformer. Commercially available Cu/ZnO/Al2O3 catalyst was coated inside the microchannel of the unit reactor for steam reforming. Pt/Al2O3 pellets prepared by ‘incipient wetness’ were filled in the cavity reactor for catalytic combustion. Those unit reactors were integrated to develop the fuel processor and operated at different reaction conditions to optimize the reactor performance, including methanol steam reformer and methanol catalytic combustor. The optimized fuel processor has the dimensions of 60 mm × 40 mm × 30 mm, and produced 450sccm reformed gas containing 73.3% H2, 24.5% CO2 and 2.2% CO at 230–260 °C which can produce power output of 59 Wt.  相似文献   

4.
A kind of composite material PdZnAl(HT)/MCM-48 was synthesized by dispersing PdZnAl-type hydrotalcite (denoted as PdZnAl(HT)) on mesoporous silica MCM-48. PdZnAl(HT) was confirmed to be formed on the MCM-48 in small particles, and the small PdZnAl(HT) particles easily collapsed during increasing the temperature. A kind of novel PdZn(Al)O/MCM-48 catalyst was obtained after calcining and reducing the PdZnAl(HT)/MCM-48 precursor. PdZn alloy species were formed on the PdZnAl(HT)/MCM-48 after reducing in H2 at 673 K. PdZn(Al)O/MCM-48-2 (with a mass ratio of PdZn(Al)O to MCM-48 = 1) had a large BET surface area (431 cm2 g?1) and small size of PdZn particles (4.1 nm) at the same time. In the steam reforming of methanol, the catalytic stability of PdZn(Al)O/MCM-48-2 was much higher than that of the Cu-based catalyst CuZn(Al)O at 503 K. The methanol conversion over PdZn(Al)O/MCM-48-2 greatly increased with increasing reaction temperature and reached 99% at 513 K. PdZn(Al)O/MCM-48-2 showed higher catalytic activity than PdZnAl(HT) and PdZn/MCM-48 (imp) at the same reaction temperature. The initial CO2 selectivity and H2 selectivity over PdZn(Al)O/MCM-48-2 at 503 K were 99.6 and 99.4%, respectively. Moreover, PdZn(Al)O/MCM-48-2 showed the highest rate of H2 production among various catalysts in the steam reforming of methanol. In a long-time operation, the methanol conversion over PdZn(Al)O/MCM-48-2 decreased from 75.8 to 68.5% after 50 h on stream at 503 K. The size of PdZn particles did not increase after 50 h on stream but the carbonaceous deposits on the catalyst surface caused the deactivation. The deactivated catalyst could be regenerated by calcining in the air at 723 K followed by reducing in the H2 at 673 K. The carbonaceous deposits were eliminated by calcining in the air and the PdZn active species were formed again by reducing in H2.  相似文献   

5.
A novel catalyst precursor ZnAl-LDHs/γ-Al2O3 was prepared by in-situ synthesis method, and the copper was supported on calcined hydrotalcite catalyst precursor by wet impregnation. The correlation between the structure and the catalytic activity for methanol steam reforming was studied by XRD, SEM, TPR, chemisorption N2O, IR and N2 adsorption techniques. The results showed that the ZnAl-LDHs was successfully synthesized by in-situ synthesis method on γ-Al2O3 and the copper mass fraction had a great effect on the interactions between support and copper species. Furthermore, the catalyst reducibility and copper surface area evidently influenced catalytic activity for methanol steam reforming. The 10% Cu/γ-Al@MMO exhibited the best catalytic activity, that was, the methanol conversion was 99.98% and the CO concentration was only 0.92% at 300 °C in hydrogen production by methanol steam reforming.  相似文献   

6.
Packed bed tube reactors are commonly used for hydrogen production in proton exchange membrane fuel cells. However, the hydrogen production capacity of methanol steam reforming (MSR) is greatly limited by the poor heat transfer of packed catalyst bed. The hydrogen production capacity of catalyst bed can be effectively improved by optimizing the temperature distribution of reactor. In this study, four types of reactors including concentric circle methanol steam reforming reactor (MSRC), continuous catalytic combustion methanol steam reforming reactor (MSRR), hierarchical catalytic combustion methanol steam reforming reactor (MSRP) and segmented catalytic combustion reactor with fins (MSRF) are designed, modeled, compared and validated by experimental data. It was found that the maximum temperature difference of MSRC, MSRR, MSRP and MSRF reached 72.4 K, 58.6 K, 19.8 K and 11.3 K, respectively. In addition, the surface temperature inhomogeneity Uf and CO concentration of the MSRF decreased by 69.8% and 30.7%, compared with MSRC. At the same reactor volume, MSRF can achieve higher methanol conversion rate, and its effective energy absorption rate is 4.6%, 3.9% and 2.6% higher than that of MSRC, MSRR and MSRP, respectively. The MSRF could effectively avoid the influence of uneven temperature distribution on MSR compared with the other designs. In order to further improve the performance of MSRF, the influences of methanol vapor molar ratio, inlet temperature, flow rate, catalyst particle size and catalyst bed porosity on MSR were also discussed in the optimal reactor structure (MSRF).  相似文献   

7.
In this present work, the delafossite type CuCr1-xFexO2 (x = 0–1) nanopowder was prepared by a self-combusted glycine nitrate process used for the steam reforming of methanol (SRM). The effectiveness of hydrogen production was upgraded by the preparation of CuCr1-xFexO2 (x = 0–1). The prepared Cu based materials were characterized by field emission scanning electron microscope studies, X-ray diffraction studies, energy dispersive X-ray studies, and Brunauer-Emmett-Teller studies. The CuCr1-xFexO2 (x = 0–1) nanopowders were studies by the hydrogen production by methanol steam reforming reaction. The Cu based catalyst exhibited high catalytic activity and hydrogen production rate as 1740 ml/min g-cat at 360 °C. Furthermore, the catalyst nanopowder was stable up to 1200 min without any considerable changes in steam reforming methanol and product selectivity in the SRM process. The production rate of CuCr1-xFexO2 was improved by the adequate amount of iron incorporation (60%) and adjusted the feeding rate of methanol. These conditions obtain the best performance could reach the hydrogen production of 301.45 (μmol (min g-cat)−1) at 350° over CuCr0.4Fe0.6O2 with a flow rate of 60 sccm.  相似文献   

8.
The metal-oxide interaction has been considered as an effective factor for catalytic performance in methanol steam reforming. In this work, Ti modified Cu/γ-Al2O3/Al catalyst was prepared by anodization technology. It is found that the addition of Ti can largely increase the surface area of the carrier and thus improve the dispersion of copper. The co-existence of Ti4+ and Ti3+ makes the charge transfer between Cu and Ti easier, which improves the redox performance of copper. The DFT calculations reveal that Ti also enhance the adsorption capacity of water and methanol on the surface of the catalysts. Besides, Ti also reduce the acid density on the carrier, inhibit methanol dehydration reaction and thereby reduce the selectivity of the DME. The optimal catalyst CuTi1.9/γ-Al2O3/Al achieves nearly 100% conversion at 275 °C, while the methanol conversion of Cu/γ-Al2O3/Al is 82%. And the H2 output of CuTi1.9/γ-Al2O3/Al reached 69.17 mol/(kgcat·h) at 300 °C.  相似文献   

9.
Hydrogen production from methanol rather than the traditional source, methane, is considered to be advantageous in ease of transportation and storage. However, the current copper-based catalysts utilized in methanol steam reforming are associated with challenges of sintering at high temperature and production of CO which could poison fuel cells. In addressing these challenges, ZnO nanorods were grown hydrothermally on the surface of cordierite and impregnated with Cu to produce catalysts for methanol steam reforming. The catalysts were characterized using SEM, XRD, FTIR, XPS, BET and Raman Spectroscopy. A fixed-bed reactor was used for testing the catalysts while the reaction products were characterized using a GC fitted with FID and TCD. The effects of temperature, methanol concentration and particle size of catalysts on methanol steam reforming were investigated. The experiments were carried out between 180 and 350 °C. CO selectivity of 0% was observed for temperatures between 180 and 230 °C for 0.8 MeOH:1H2O with an average H2 selectivity of 98% for that temperature range. XPS showed that the catalyst was relatively unchanged after reaction while Raman spectroscopy revealed coke formation on the catalyst surface for reactions carried out above 300 °C. This shows that the catalyst is active and selective for the reaction.  相似文献   

10.
A series of ZnO–Al2O3 catalysts with various ZnO/(ZnO + Al2O3) molar ratios have been developed for hydrogen production by dimethyl ether (DME) steam reforming within microchannel reactor. The catalysts were characterized by N2 adsorption-desorption, X-ray diffraction and temperature programmed desorption of NH3. It was found that the catalytic activity was strongly dependent on the catalyst composition. The overall DME reforming rate was maximized over the catalyst with ZnO/(ZnO + Al2O3) molar ratio of 0.4, and the highest H2 space time yield was 315 mol h−1·kgcat−1 at 460 °C. A bi-functional mechanism involving catalytic active site coupling has been proposed to account for the phenomena observed. An optimized bi-functional DME reforming catalyst should accommodate the acid sites and methanol steam reforming sites with a proper balance to promote DME steam reforming, whereas all undesired reactions should be impeded without sacrificing activity. This work suggests that an appropriate catalyst composition is mandatory for preparing good-performance and inexpensive ZnO–Al2O3 catalysts for the sustainable conversion of DME into H2-rich reformate.  相似文献   

11.
In this experimental study, a membrane reactor housing a composite membrane constituted by a thin Pd-layer supported onto Al2O3 is utilized to perform methanol steam reforming reaction to produce high-grade hydrogen for PEM fuel cell applications. The influence of various parameters such as temperature, from 280 to 330 °C, and pressure, from 1.5 to 2.5 bar, is analyzed. A commercial Cu/Zn-based catalyst is packed in the annulus of the membrane reactor and the experimental tests are performed at space velocity equal to 18,500 h−1 and H2O:CH3OH feed molar ratio equal to 2.5:1. Results in terms of methanol conversion, hydrogen recovery, hydrogen yield and products selectivities are given. As a best result of this work, 85% of methanol conversion and a highly pure hydrogen stream permeated through the membrane with a CO content lower than 10 ppm were reached at 330 °C and 2.5 bar. Furthermore, a comparison between the experimental results obtained in this work and literature data is proposed and discussed.  相似文献   

12.
Alumina prepared by the sol-gel method, was impregnated with zirconia (5, 15 and 30 wt.%). Subsequently, the resulting Al2O3–ZrO2 supports were impregnated with 15% Ni to obtain the Ni/Al2O3–ZrO2 catalysts. The obtained catalysts were characterized by BET, SEM, XRD, H2-TPR and TPD- CO2. The catalytic activity was studied by means of dry reforming of methane (DRM) for syngas production. The catalysts displayed different physicochemical properties and trends of their catalytic activity as a function of the ZrO2 content in the mixed oxide supports. For instance, ZrO2 (5 wt %) in the catalyst, led to enhanced concentration of the medium strength basic sites and increased specific surface area, yielding thus the best performance in the DRM, with low carbon deposition after 36 h of reaction, compared with the other catalysts. This indicates that during the DRM reaction, this catalyst can provide more surface oxygen to prevent carbon deposits that could deactivate the catalyst.  相似文献   

13.
Electricity generation for mobile applications by proton exchange membrane fuel cells (PEMFCs) is typically hindered by the low volumetric energy density of hydrogen. Nevertheless, nearly pure hydrogen can be generated in-situ from methanol steam reforming (MSR), with Cu-based catalysts being the most common MSR catalysts. Cu-based catalysts display high catalytic performance, even at low temperatures (ca. 250 °C), but are easily deactivated. On the other hand, Pd-based catalysts are very stable but show poor MSR selectivity, producing high concentrations of CO as by-product. This work studies bimetallic catalysts where Cu was added as a promoter to increase MSR selectivity of Pd. Specifically, the surface composition was tuned by different sequences of Cu and Pd impregnation on a monoclinic ZrO2 support. Both methanol conversion and MSR selectivity were higher for the catalyst with a CuPd-rich surface compared to the catalyst with a Pd-rich surface. Characterization analysis indicate that the higher MSR selectivity results from a strong interaction between the two metals when Pd is impregnated first (likely an alloy). This sequence also resulted in better metallic dispersion on the support, leading to higher methanol conversion. A H2 production rate of 86.3 mmol h?1 g?1 was achieved at low temperature (220 °C) for the best performing catalyst.  相似文献   

14.
Three metal-organic frameworks Cu-BTC, Zn-BTC, and Cu/Zn-BTC were prepared and impregnated in nitrate solutions to obtain the precursors. After calcination, three metal-BTC-derived CuO/ZnO/CeO2/ZrO2 catalysts were obtained. The samples were characterized and the catalyst-coated cordierite honeycomb ceramics were used in a microreactor for methanol steam reforming at different reaction conditions. Results showed that the Cu/Zn-BTC-derived catalyst exhibited the most fine and uniform particles, the best reducibility, the largest specific surface area, and the optimal surface elemental state due to the difference in the formation mechanisms, resulting in its remarkable catalytic performance. The ceramic support coated with Cu/Zn-BTC-derived catalyst could achieve 100% methanol conversion rate and 0.336 mol/h H2 output at 260 °C in the microreactor. Stability tests demonstrated that the Cu/Zn-BTC-derived catalyst could maintain its excellent performance without deactivation within 30 h continuous reaction, which was connected with the Ce–Zr–O solid solution with high concentration of oxygen vacancies and surface oxygen.  相似文献   

15.
The synthesized novel metal oxides YxCeyRuzO4 (x = 1.5, y = 0.84, z = 0.04) which was produced by the sol-gel method was used as a support for Cu active metal on the surface of a microchannel plate reactor in the methanol steam reforming (MSR) process. The prepared catalysts were characterized by X-ray powder diffraction (XRD), BET surface area analysis (SBET), energy-dispersive X-ray analysis (EDX), field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), temperature-programmed desorption (NH3-TPD), and temperature-programmed reduction (H2-TPR). High methanol conversion (99.5%) and H2 selectivity (98.7%) and low CO selectivity (1.4%) were achieved for Cu/YxCeyRuzO4 coated microchannel reactor at 250 °C. FE-SEM images and TGA curve of the spent catalyst displayed no coke formation on the surface of the catalyst after 32 h on stream at 300 °C. The low reduction temperature of Cu, high BET surface area, and high pore volume of the catalyst are considered imperative factors that cause a better dispersion of copper on the Y1.5Ce0.84Ru0.04O4 support.  相似文献   

16.
The effect of metal oxide (CeO2, Al2O3 and ZrO2) support and In2O3 co-supported Pt catalysts has been investigated on steam reforming of methanol in microreactors. CeO2, Al2O3 and ZrO2 were prepared by the sol-gel method and they were used as a support, which was impregnated with In2O3 as co-support followed by the introduction of Pt species via the wet impregnation method. The size and dispersion of the Pt nanoparticles on In2O3/support have been examined by transmission electron microscopy. From these TEM and XPS results, it was found that the addition of In2O3 supports the formation of a high concentration of metallic Pt nanoparticles with enhanced dispersion and controlled particle size on the surface. The activity and stability of all the developed catalysts were tested for the steam reforming of methanol in microreactors at different temperatures. Under reforming conditions without prior reduction, a Pt/CeO2 catalyst containing 15 wt % of Pt exhibited complete methanol conversion and high selectivity towards hydrogen at 350 °C. However, the CO formation was found to be very high (7.0 vol %) for this catalyst. Upon addition of In2O3 as a co-support to this formulation the formation of CO decreased considerably. Pt/In2O3/CeO2 catalyst containing 15 wt % of Pt and 15 wt % of In2O3 showed excellent catalytic performance at much lower concentration of CO. This change could be closely associated with the formation of metallic Pt nanoparticles with smaller size, higher dispersion with strong interaction between Pt, In2O3 and support, which creates more oxygen vacancies to activate the water molecule which then react with methanol to produce H2 and CO2 suppressing the CO formation. Moreover, CeO2 supported Pt/In2O3 catalyst displayed higher stability with lowest CO formation under continuous steam reforming operation of 100 h. The superior performance of this catalyst is thought to be due to the relative abundance of redox sites on the CeO2 surface, which is able to create an oxygen vacancy as it possesses higher oxygen storage capacity and oxygen exchange capacity. This work demonstrates that the nature of support plays a crucial role for the continuous activation of reactants and determines the catalytic stability during methanol steam reforming.  相似文献   

17.
Steam reforming of methanol was investigated over Cu–ZnO–ZrO2–Al2O3 catalysts at 473 and 573 K. The Cu:Zn:(Al + Zr) molar ratio was 3:3:4; however, the Zr:Al molar ratio was varied and the catalysts were pretreated at different calcination and reduction temperatures. The synthesized catalysts were characterized by N2 physisorption, temperature-programmed reduction with H2 (H2-TPR), X-ray diffraction, oxidized surface TPR, and infrared spectroscopy after carbon monoxide chemisorption. The crystalline size of Cu decreased on increasing the calcination temperatures from 573 to 623 K and increased on increasing the reduction temperatures from 523 to 573 K. Among the tested catalysts, the Cu–ZnO–ZrO2 catalyst exhibited the highest and lowest hydrogen-formation rates at 473 and 573 K, respectively. After the reaction at 573 K, all the tested catalysts exhibited an increase in the Cu crystalline size, causing the catalyst deactivation. Among the tested catalysts, the Cu–ZnO–ZrO2–Al2O3 catalyst, where the Cu:Zn:Al:Zr molar ratio was 3:3:2:2, showed the highest and most stable catalytic activity at 573 K. Cu dispersion and catalyst composition affected the catalytic performance for steam reforming of methanol.  相似文献   

18.
Utilizing a compact, efficient and fast-response reactor for on-site reforming of liquid methanol is an effective method to solve the storage and transportation problems of hydrogen. In this paper, a mesh-type structured CuFeMg/γ-Al2O3/Al catalyst with strong bonding force was prepared by anodic oxidation method, and its intrinsic catalytic activity, hydrogen production capacity and start-up performance were compared with commercial granular catalyst in a plate microreactor. The results showed that although the mesh-type structured catalyst displayed lower intrinsic activity, it exhibited higher methanol conversion, which was because of the enhanced mass transfer ability. Overall, for the mesh-type structured catalyst, 27.1% higher hydrogen production capacity per unit volume was achieved when methanol conversion was 90%, and the reactor start-up time was reduced by 16.1% owing to the high thermal conductivity of the aluminum substrate. Moreover, the mesh-type structured catalyst also showed excellent stability in 160 h test.  相似文献   

19.
This study is focused on investigating the dual performance of Rh/CeO2/γ-Al2O3 catalyst for steam reforming of ethanol (SRE) and thermochemical water splitting (TCWS) using a packed bed reactor. The catalyst is designed to be thermally stable containing an active phase of Rh and the redox component of CeO2 for oxygen exchange, supported on γ-Al2O3. The catalyst has been characterised by SEM, XRD, BET, TPR, TPD, XPS and TGA before testing in the reactor. The optimal temperature for SRE reaction over this catalyst is between 700 °C and 800 °C to produce high concentrations of hydrogen (~60%), and low CO and CH4. The selectivity towards CO and CH4 is higher at low temperatures and drops with rise in reaction temperature. Further, Rh/CeO2/γ-Al2O3 is found to be active for TCWS at relatively low temperatures (≤1200 °C). At temperatures as low as 800 °C, this catalyst is especially found suitable for multiple redox cycles, producing a total of 48.9 mmol/gcat in four redox cycles. The catalyst can be employed for large number of redox cycles when the reactor is operated at lower temperatures. Finally, the reaction pathways have been proposed for both SRE and TCWS on Rh/CeO2/γ-Al2O3 catalyst.  相似文献   

20.
This paper presents an investigation concerning the reforming of methanol over various base-metal oxide catalysts. Copper-based catalysts were effective for the steam reforming of methanol. The selectivity and conversion was studied in a flow reactor in the temperature interval 180–320°C. The active materials were impregnated on γ-alumina pellets using the wet impregnation method. The promoters used in the investigation were chromium (Cr), zinc (Zn) and zirconia (Zr). The copper content and promoter used played an important role in the catalyst's ability to selectively convert methanol at low temperatures. Catalysts with high copper contents generally gave higher conversions and selectivities for the steam reforming reaction. The use of ternary components generally increased the catalyst selectivity towards carbon dioxide. Zirconia had a positive influence on the catalytic performance at low temperatures. The possibilities for the use of reforming systems with copper-based catalysts in fuel cell applications are promising.  相似文献   

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