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1.
To decompose dimethylhexane-1,6-dicarbamate (HDC) to hexamethylene diisocyanate (HDI), mixed CuO and ZnO catalysts with Cu/(Cu?+?Zn) ratio of 4 and 8% were prepared by coprecipitation (CP), sequential precipitation (SP) and incipient wetness impregnation (IW). The SP-derived CuO/ZnO catalysts showed higher HDC yields than those derived by CP and IW. The IW method produced CuO/ZnO catalysts consisting of larger CuO and ZnO particles compared to the two precipitation methods. The CP method led to substitution of Zn2+ by Cu2+ in the hydrozincite precursor phase, resulting in higher BET and Cu surface areas of CuO–ZnO catalysts due to intimate intergrowth of nano-sized particles. However, the inherent character of ZnO in the CP-derived catalysts was modified by interfacial contact between CuO and ZnO identified by UV–visible and Raman spectra. In contrast, the properties of CuO and ZnO, as well as the relatively large surface areas, were kept in the SP-derived catalysts owing to deposition of Cu precipitates to fully aged Zn precipitates. This is believed to be a benefit of the SP method for the reaction. Therefore, our preparation approach has great potential to be extended to various mixed oxide catalysts.  相似文献   

2.
A set of mono-and bimetallic(Zn-Co) supported ZSM-5 catalysts was first prepared by PEG-additive method. The physicochemical properties of the catalysts were investigated by FTIR, XPS, XRD, N_2adsorption-desorption measurements, SEM, EDS and NH3-TPD techniques. The physicochemical properties showed that the Zn Co_2O_4 spinel oxide was formed on the ZSM-5 support and provided effectual synergetic effect between Zn and Co species for the bimetallic catalyst. Furthermore, bimetallic supported ZSM-5 catalyst exhibited weak, moderate and strong acidic sites, while the monometallic supported ZSM-5 catalyst showed only weak and moderate or strong acidic sites. Their catalytic performances for thermal decomposition of hexamethylene–1,6–dicarbamate(HDC) to hexamethylene–1,6–diisocyanate(HDI) were then studied. It was found that the bimetallic supported ZSM-5 catalysts,especially Zn-2Co/ZSM-5 catalyst showed excellent catalytic performance due to the good synergetic effect between Co and Zn species, which provided a suitable contribution of acidic sites. HDC conversion of 100% with HDI selectivity of 91.2% and by-products selectivity of 1.3% could be achieved within short reaction time of 2.5 h over Zn-2Co/ZSM-5 catalyst.  相似文献   

3.
Zn取代类水滑石衍生复合氧化物上N2O的催化分解   总被引:2,自引:1,他引:1  
恒定二价与三价阳离子比为3((nZn+nMg)/nAl=3), 采用共沉淀法制备不同Zn含量的系列类水滑石前驱物ZnxMg3-xAl-HT (x=0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0), 经焙烧得到其衍生复合氧化物催化剂ZnxMg3-xAlO, 用于N2O的直接催化分解. 采用X射线衍射(XRD)、比表面积分析(Brunauer-Emmett-Teller)、热分析(TG-DSC)和傅里叶变换红外(FT-IR)光谱等表征手段考察了Zn含量对材料前驱物及其衍生复合氧化物组成和结构的影响, 研究了系列ZnxMg3-xAlO催化剂的N2O催化分解性能, 同时探讨了反应条件, 如N2O浓度、空速、O2和H2O等因素对催化剂活性的影响. 结果表明, 所有前驱物材料均能形成完整的层状水滑石结构; 经高温焙烧后形成了以Zn-Al尖晶石为主相的复合氧化物, 且Zn掺杂有助于促进尖晶石相的生成; Zn含量对材料的热稳定性、比表面积和N2O催化分解活性有显著的影响; 随着Zn含量增加, 催化剂比表面积下降, 但其不是影响催化剂活性的主要因素; 650 ℃焙烧后的Zn2.0Mg1.0AlO催化剂具有较好的N2O催化分解活性; N2O浓度、空速及O2对催化剂活性的影响较小, 而H2O则对活性有较大的影响.  相似文献   

4.
This paper reports on a novel processing route for producing ZnO nanoparticles by solid-state thermal decomposition of zinc(II) acetate nanostructures obtained by the sublimation of zinc(II) acetate powder. The sublimation process of the Zn(OAc)2 powder was carried out in the temperature 150 °C for 2 h. In addition, nanoparticles of ZnO were obtained by solid-state thermal decomposition of the synthesized Zn(OAc)2 nanostructures. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, and energy dispersive X-ray spectroscopy. The sublimation process of the Zn(OAc)2 powder was carried out within the range of 150–180 °C. The XRD studies indicated the production of pure hexagonal ZnO nanoparticles after thermal decomposition.  相似文献   

5.
Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M(Cu,Zn)-ammonia complexes (DMAC) at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol (212 g/(Lcat·h);T=513 K,p=3MPa,SV=12000 h-1).  相似文献   

6.
In this study, COx-free hydrogen production via methane decomposition was studied over Cu–Zn-promoted tri-metallic Ni–Co–Al catalysts. The catalysts have been prepared by the constant pH co-precipitation method, and the nominal Ni metal loading was fixed at 50 wt % along with other metals at 10 wt% each. The catalyst activity for methane decomposition reaction was examined in a reactor between 400 °C and 700 °C and at atmospheric pressure. Different techniques such as N2-physisorption, X-ray diffraction, H2-TPR SEM, TEM, ICP-MS, TGA, and Raman spectroscopy were applied to characterize the catalysts. The relation between the catalyst composition and their catalytic activity has been investigated. The controlled synthesis has resulted in a series of catalysts with a high surface area. Ni–Co–Cu–Zn–Al was the most active and productive catalyst. Various characterizations indicate that the promotional effects of Cu–Zn interaction were the critical factor in catalysts' activity and stability. Ni–Co–Cu–Zn catalyst gave the highest methane conversion of 85% at 700 °C. Zn addition improves the stability of the catalyst by retaining the active metal size during the decomposition reaction. The catalyst was active for 80 h of stability study. The rapid deactivation of the Ni–Co catalyst was due to the sintering of the catalyst at 650 °C. Moreover, carbon species accumulated during the methane decomposition reaction depend on the catalysts' composition. Zn promotes the growth of reasonably long and thin carbon nanotubes, whereas the diameter of carbon nanotubes on unpromoted catalysts was large.  相似文献   

7.
8.
采用低温N2吸附、XRD、MES、CO-TPR和H2-DTG研究了Zn(100 gFe/x gZn, x=7~100)助剂对 Fischer-Tropsch (F-T) 合成Fe基催化剂的织构性质、还原行为以及相变结构的影响;在H2/CO=2.0、260 ℃、1.5 MPa和4000 mL/(g·h) 条件下在固定床反应器上考察了Zn助剂含量对Fe基催化剂F-T合成反应活性、烃产物选择性和运行稳定性的影响。研究结果表明,随着Zn含量的增加,氧化态催化剂的物相由α-Fe2O3和ZnFe2O4逐渐向ZnFe2O4和ZnO转变,ZnFe2O4在催化剂中优先生成,只有在超出其计量比1∶2之后才有ZnO出现。由于ZnFe2O4较为稳定,能够促进催化剂中Fe物相的分散,导致比表面积增加。在还原和反应态催化剂中,ZnFe2O4一方面抑制催化剂的过度还原和碳化;另一方面表现为稳定活性相铁碳化物。催化剂的F-T反应性能评价结果表明,纯铁催化剂由于铁碳化物氧化而迅速失活,而Zn助剂催化剂却由于ZnFe2O4的稳定作用,活性较为稳定。同时,由于催化剂在反应初相变的影响,导致Zn助剂催化剂的初始烯烃选择性随着Zn含量的增加而增加,在相态稳定之后选择性趋于一致。  相似文献   

9.
Chlorophenols are widely used as industrial chemicals such as herbicides, insecticides, wood preservatives, and disinfectants. However, chlorophenols are very toxic materials and they have become the cause of current environmental issues. Hydrodechlorination (HDC) reaction is a more environmentally friendly removal method of chlorophenols than other methods. In this paper, Pd–modified graphene was prepared and applied to HDC reaction. Pd supported on graphene (refer to Pd/G) was prepared using the recently reported microwave irradiation method. The Pd(II)/GO was made by impregnation methods of palladium precursors in solution phase and was subsequently reduced to Pd/G by microwave irradiation. The morphological and chemical structure of the Pd/G was characterized by XRD, SEM, ICP-MS, EDS, and TEM. It was found that the graphene-based Pd catalyst showed the highest catalytic performance among Pd/Y, Pd/MCM-41, and Pd/G catalysts. This is attributed to the smaller particle size and higher dispersions of Pd nanoparticles on the graphene surface. The catalytic HDC of chlorophenols was investigated. For HDC reaction, 100 ppm solution of chlorophenols such as 4-chlorophenol, six isomers of dichlorophenol, and 2,3,5-trichlorophenol in isopropanol was treated with catalyst and base, such as Na2CO3 and K2CO3, under a hydrogen gas at ambient pressure. The progress of the chlorophenol decomposition was analyzed with GC. All chlorophenols were completely decomposed within 2 h in the 3 % Pd/G catalyst. The reaction pathway of chlorophenols was elucidated from the conversion of chlorophenols and selectivities of products. The reuse of the catalyst was also studied. The performance of the recycled catalyst in HDC reaction up to six successive runs was observed.  相似文献   

10.
采用浸渍法对无定形ZnO分别用稀H2SO4和(NH4)2S2O8溶液处理, 制备了SO42-/ZnO和S2O82-/ZnO固体酸. 通过固体离子交换法制备了Cu(Ⅰ)/SO42-/ZnO和Cu(Ⅰ)/S2O82-/ZnO两种催化剂, 并采用XRD, FTIR, TPD和TPR等进行了表征. 研究结果表明, 用稀H2SO4和(NH4)2S2O8溶液分别浸渍处理无定形ZnO, 经过500-600 ℃高温焙烧后得到的SO42-/ZnO和S2O82-/ZnO固体酸表面形成了Zn3O(SO4)2物种; py-FTIR结果表明, 两者均具有B酸中心和L酸中心, 进一步的NH3-TPD研究结果证明, 制备的固体酸NH3脱附峰均出现在543 ℃附近, 属于高强度固体酸. 结构分析认为, 由于SO42-强烈的电子诱导作用, SO42-和ZnO形成的桥式配位物种产生了B酸中心和L酸中心, 而其螯合配位形成的物种没有酸性. SO42-/ZnO和S2O82-/ZnO固体酸与CuCl进行离子交换所制备的Cu(Ⅰ)/SO42-/ZnO和Cu(Ⅰ)/S2O82-/ZnO催化剂的Cu(Ⅰ)易于还原, 对甲醇氧化羰基化合成碳酸二甲酯(DMC)表现出较高的活性和选择性, DMC选择性为98.3%, 时空收率可达到1.9 g(g·h).  相似文献   

11.
宗玥 《分子催化》2014,(4):336-343
将导热性能良好的泡沫铝作为载体,羰基钌为前驱体制备了一系列不同形态的钌基催化剂应用于N2O的低温催化分解研究.采用XRD、XPS、SEM、TEM、BET、H2-TPR等方法对催化剂进行了表征,于石英管固定床反应器上对催化剂性能进行了评价.重点考察了泡沫铝作为催化剂载体的可行性、载体的处理方法对催化剂活性的影响以及RuO2、Ru、Ru3(CO)12所表现出的活性差异.结果表明:泡沫铝作为催化剂载体,能够促进N2O的催化分解;泡沫铝经H2O2处理有利于提高其对活性中心的附着力,提高催化活性;N2O浓度为1%,Ru负载量为0.3%,活性中心分别为Ru3(CO)12、Ru、RuO2时,N2O完全转化温度依次为285、380和415℃;活性较高的Ru3(CO)12/泡沫铝催化剂在长时间作用后活性组分转变为RuO2.  相似文献   

12.
Hydrodechlorination (HDC) reaction of chlorophenols was carried out using Pd catalysts supported over zeolite Y, MCM-41 or graphene. Pd-MCM-41 and Pd-Y zeolite were prepared by impregnation and ion-exchange method, respectively. Pd-graphene (Pd-G) was prepared by hydrazine hydrate reduction of palladium ion dispersed on graphene oxide. The catalysts were characterized by several analytical tools such as X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). These catalysts were subjected to HDC reaction of chlorophenols, such as 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 3,4-dichlorophenol (3,4-DCP). The reaction rate of HDC of chlorophenols catalyzed by Pd catalysts with various solid bases, such as KF/Al2O3 (alumina), sodium acetate (NaOAc) and K2CO3 was compared. First, Pd-MCM-41 and Pd-Y catalysts were compared. 2,4- and 3,4-DCPs were completely decomposed within 6 h, in the case of Pd-MCM-41 with NaOAc. Using Pd-Y instead of Pd-MCM-41 with NaOAc, much faster decomposition was observed. Faster decomposition of 4-CP and DCPs was observed with NaOAc base than K2CO3 or KF/Al2O3 under the same condition. In the case of Pd-Y with KF/Al2O3, slower decomposition of 4-CP and DCPs was observed. These base effects were interpreted using the solubility of NaCl and KCl in alcohol and the basic sites of KF/Al2O3. Because the solubility of NaCl is known to be larger than KCl solubility in alcohol, byproduct NaCl could be easily dissolved and ionized in solvents. For Pd-Y with KF/Al2O3, the small pore size of Y zeolite can interfere with the diffusion of HCl to KF/Al2O3 basic site. Second, three catalysts, including Pd-graphene, were compared. 2,4-DCP was decomposed within 2 h using Pd-G with either K2CO3, NaOAc or KF/Al2O3. Pd-G catalyst showed the highest catalytic activity among Pd-G, Pd-MCM-41 and Pd-Y catalysts. The high activity and stability of the Pd-G could be attributed to the strong metal–support interaction with an electron-deficient site and a critical Pd particle size (ca. 3.5 nm) of Pd-G nanocatalyst with a stronger resistance to the deactivation and good affinity toward aromatic organic molecules, especially phenols. The progress of HDC reaction was monitored by gas chromatography with flame ionization detection (GC/FID), and a feasible degradation process could be explained by analyzing the degradation products such as phenol, cyclohexanone and cyclohexanol from resulting GC chromatograms. The effect of reaction temperature on HDC in Pd-G catalyst was also discussed. In conclusion, Pd-G is an efficient catalyst for decomposition of chlorophenols and can be applied to remediation of chlorophenol-contaminated water under mild conditions.  相似文献   

13.
Co-M(M=La,Ce, Fe,Mn, Cu,Cr)复合金属氧化物催化分解N2O   总被引:1,自引:0,他引:1  
薛莉  贺泓 《物理化学学报》2007,23(5):664-670
通过共沉淀法制备了一系列Co-M(M= La, Ce, Fe, Mn, Cu, Cr)复合金属氧化物及纯Co3O4催化剂, 考察了其催化分解N2O 的活性. 结果表明在研究的系列催化剂中, Co-Ce 复合氧化物催化剂具有最好的催化分解N2O的活性; 其活性与Ce/Co 摩尔比有直接的关系, 当Ce/Co 摩尔比为0.05 时(CoCe0.05 催化剂)催化活性最佳; 当有NO 和O2共存时, 可能在催化剂活性中心上形成表面硝酸盐或亚硝酸盐吸附物种而使其活性受到较大影响. 通过对Co-M 催化剂的XRD、BET、O2-TPD及H2-TPR 等表征结果的分析, 发现作为主要活性位的Co2+的氧化还原能力是影响催化剂活性的主要原因. 这是因为根据反应机理, N2O 的表面分解步骤与Co2+氧化成Co3+的能力相关, 而吸附氧的脱附与Co3+还原成Co2+的能力相关. 在所研究的催化剂中, 添加除CeO2之外的其它过渡金属氧化物时, 催化剂中Co3+/Co2+的氧化还原能力降低, 因此其催化性能降低. 另外, 添加不同过渡金属氧化物也改变了N2O 催化分解反应的速控步骤.  相似文献   

14.
A sol–gel based hybrid process was developed by manipulating different techniques in sol–gel process to synthesize γ-alumina and (CuO, CuO + ZnO) doped γ-alumina spherical particles. Catalysts having spherical geometry have an important advantage over powders or pellets which are impervious to fluids, when packed in a reactor. Boehmite sol was used as alumina precursor for synthesizing porous γ-alumina and doped materials. γ-alumina particles having 5 wt% CuO, 4 wt% CuO + 1 wt% ZnO, 3 wt% CuO + 2 wt% ZnO and 2 wt% CuO + 3 wt% ZnO were prepared by adding required amounts of Cu(NO3)2 and Zn(NO3)2 solutions prior to gelation of the sol. Methanol dehydration studies were carried out by employing these synthesized catalysts. Hundred percent conversion of methanol to dimethyl ether was observed with (4 wt% CuO + 1 wt% ZnO)-γ-alumina and (5 wt% CuO)-γ-alumina microspheres at 325 and 350 °C, respectively.  相似文献   

15.
Higher alcohol has been considered as a potential fuel additive. Higher alcohol, including C2–C4 alcohol was synthesized by catalytic conversion of syngas (with a ratio of CO/H2?=?1) derived from natural gas over modified Cu/ZnO/Al2O3 catalyst. Modified Cu/ZnO/Al2O3 catalysts promoted by alkali metal (Li) for higher alcohol synthesis (HAS) were prepared at different pH (6, 6.5, 7, 8, and 9) by co-precipitation to control Cu surface area and characterized by N2 physisorption, XRD, SEM, H2-TPR and TPD. The HAS reaction was carried out under a pressure of 45 bar, GHSV of 4000 h?1, ratio of H2/CO?=?1, and temperature ranges of 240 and 280 °C. It was found that the malachite phase of copper causes the size of copper to be small, which is suitable for methanol synthesis. Methanol and HAS share a common catalytic active site and intermediate. It was also found that the productivity to higher alcohol was correlated with Cu surface area.  相似文献   

16.
The catalytic properties of ZnAlVO mixed oxides derived from decavanadate-exchanged ZnAl–layered double hydroxide (LDH) precursors prepared by a sol–gel method (ZnAlVO–LDHx,y) were investigated in the oxidative dehydrogenation of propane and compared with those of supported catalysts obtained by conventional impregnation of NH4VO3 on ZnO (ZnVO-I,y) and ZnAlO mixed oxide (ZnAlVO-I,y) supports. The effects of composition and calcination time on the catalytic behavior were particularly examined. Higher propane conversions were achieved at higher vanadium content and calcination time of the precursors. The LDH-derived catalysts were the most active ones in all the temperature range studied (300–425 °C). The order of activity for propane conversion for the different catalyst families varies as ZnAlVO–LDHx,y > ZnAlVO-I > ZnVO-I and follows the strength of the Lewis and Brønsted acid sites determined by monitoring of pyridine adsorption by Fourier transform infrared spectroscopy, whereas the propene selectivities are close together in agreement with the similar densities of basic sites determined by CO2–temperature-programmed desorption measurements. It was indeed established that the acidity, rather than the nature of the crystalline phases, the reducibility, or the specific surface area of the samples, governs the catalytic activity.  相似文献   

17.
Calcium aluminate (12CaO–7Al2O3) powder was synthesized using three methods, viz. Pechini, coprecipitation, and a new novel facile decomposition route starting from activated alumina and calcium nitrate precursors, then used as a support to prepare a series of 31 wt%Ni/12CaO–7Al2O3 catalysts by deposition–precipitation method. The resultant catalysts were tested in steam pre-reforming of natural gas at 400–550 °C, low steam-to-carbon (S/C) molar ratio of 1.5, and atmospheric pressure. The obtained samples were characterized by Brunauer–Emmett–Teller (BET) analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), hydrogen chemisorption, and CO2–temperature-programmed desorption (TPD). Experimental results showed that the basicity and morphology of the supports depended significantly on the synthesis method. Calcium aluminate synthesized using the new decomposition procedure showed surface area of 6.23 m2 g?1, while the surface area of those prepared by the Pechini and coprecipitation method were 1.38 and 3.76 m2 g?1, respectively. The catalytic properties of the 31 wt%Ni/12CaO–7Al2O3 catalysts were strongly influenced by the support preparation approach. The highest specific surface area (about 230 m2 g?1), smallest Ni particle size (8.86 nm), and highest nickel dispersion (7.48%) were observed for the catalyst whose support was synthesized by the decomposition method. Even at high gas hourly space velocity (GHSV) of 2 × 105 mL \({\text{g}}^{ - 1}_{\text{catalyst}}\) h?1, this catalyst exhibited around 100% C2H6 and C3H8 conversion at temperature above 500 °C. High catalytic stability during 60 h time on-stream was also shown. The TPO profiles of the spent catalyst demonstrated high resistance to carbon formation.  相似文献   

18.
刘畅  薛莉  贺泓 《物理化学学报》2009,25(6):1033-1039
采用低温柠檬酸络合法制备了添加不同碱土金属的钴铈复合氧化物(Ce/Co摩尔比为0.05)催化剂, 考察了其催化N2O分解的活性. 结果表明, 碱土金属对钴铈催化剂催化N2O分解的活性有明显促进作用, 助催化效果递变顺序为Mg相似文献   

19.
The ZnO–ZnCr2O4 (Zn–Cr–O) sample obtained by decomposition of Zn-Cr hydrotalcite precursor was subjected to the thermal treatment at different temperatures and the physico-chemical properties of the Zn–Cr–O system were compared with its catalytic behavior in dehydrocyclization of crude glycerol and ethylenediamine (EDA). Upon high temperature treatment of Zn–Cr–O the Cr6+ ions underwent autoreduction to form stable Cr3+ species and the particle size of both ZnO and ZnCr2O4 increased dramatically. Thermal effect did not influence the intermolecular cyclisation of EDA to form pyrazine. By contrast, an inversely proportional dependence was found between the rate of formation of 2-methylpyrazine and the particle size of Zn–Cr–O whereas the rate of 2-pyrazinylmethanol was directly proportional to the particle size.  相似文献   

20.
采用浸渍法制备了Pd促进ZnO/Al2O3催化剂, 考察了该催化剂作用时, 在水醇摩尔比为3, 常压和450 °C工作条件下乙醇水蒸气重整(SRE)制氢反应性能. 研究结果表明, 在该催化剂体系作用下的SRE反应过程中, H2、CH3CHO为主要产物, 与ZnO/Al2O3催化剂不同, Pd能促使CH3CHO发生C-C键断裂反应, 显著提高C2H5OH转化率及H2选择性, 分别达65%、55%. 还利用BET比表面积、透射电子显微镜(TEM)、热重-差示扫描量热-质谱(TG-DSC-MS)等表征手段考察了催化剂失活以及表面积炭情况, 发现Pd的加入对催化剂总积炭量并无明显影响.  相似文献   

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