不同焙烧气氛对氧化镁表面碱性的影响

The MgO samples are prepared by heating Mg(OH) 2 at 600 ℃ in different atmospheres. The XRD results show that Mg(OH) 2 is decomposed into MgO after calcination. The results of BET indicate that the specific surface area of the samples is affected by the calcination atmosphere, the sample preheated in vacuum has the highest surface area, while the sample preheated in air has the lowest surface area. The CO 2 TPD profiles of the samples are also different, which implies that the samples have different surface basicity. From the desorbed amount of CO 2 and the desorption activation energy, it is found that the sample pretreated in vacuum has the most basic sites and the strongest basicity.     

Preparation, Characterization of Hydrotalcites and the Catalytic Properties in Synthesis of o-Phenylphenol over Pt／CHT

Mg/Al mixed oxides with molar ratios of 2-6 of Mg to Al used as supports for platinum catalysts were obtained by the thermal decomposition method. The effect of the composition of the mixed oxides on the physicochemical properties was studied by TPD, nitrogen sorption, XRD and TG-DTA characterization methods. The synthesis of o-phenylphenol (OPP) from a dimer (obtained from cyclohexanone condensation) was investigated over Pt/CHT catalysts and compared with those over Pt/MgO and Pt/Al2O3 catalysts. These catalysts show a high activity and selectivity for OPP, with a conversion reaching 93.8% and a selectivity reaching 87.9% in some experiments. For Pt/CHTx catalysts, the calcined hydrotalcites exhibited strong base sites, which were necessary to catalyze the synthesis of OPP.     

Reforming of CH4 with CO2 over Co/Mγ-Al oxide catalyst

A series of Co/Mg–Al oxide samples,CoMgAl-x(x=(Mg+Co)/Al molar ratio of 1–5),were prepared by the self-combustion method followed by H2reduction.The catalytic performance and stability of the samples were studied in dry reforming of CH4.XRD and H2-TPR characterization results showed that the reduced CoMgAl-x samples mainly consisted of solid solution and spinel phases with cobalt particles.The spinel phases contained Co3O4 and Con Mg1-n Al2O4(0≦n≦1)varying with the(Mg+Co)/Al ratio.The effect of (Mg+Co)/Al molar ratio on the catalytic behavior was investigated in detail and CoMgAl-3 exhibited the highest catalytic activity and stability among the catalysts studied.     

Structure and Catalytic Behaviour of Saponite and Its Cross-Linking Product

Synthetic saponites have been intercalated with hydroxyl aluminium oligomers and characterized with several techniques. The basal 001 peak of the pillared saponite (PS) is 1. 8 nm. The amount of the aluminium in the tctrahedral sheet is correlative with cross-linking density. The sheet-to-pillar linkage mode may be Si-O-AlpⅥ. The acid sites in pillared saponite may locate either at surface of clay or at that of pillar. The cumene conversion is relative to accessible acid sites on the surface of PS. The pillar density in the PS has an effect on the pore structure which is correlative with shape selectivity during the reaction between ethanol and ammonia.     

Effects of ammonium exchange and Si/Al ratio on the conversion of methanol to propylene over a novel and large partical size ZSM-5

One type of ZSM-5 zeolite with large partical size was prepared and characterized by XRD, SEM, N2 adsorption-desorption, XRF, Py-IR and NH3-TPD techniques. Effects of ammonium exchange and SiO2/Al2O3 molar ratios on the reaction of methanol to propylene (MTP) over Na-ZSM-5 and H-ZSM-5 zeolites have been studied in a fixed-bed flow reactor under the operating conditions of T = 500 °C, P = 1 atm, and WHSV = 6 h-1. Ammonium exchange led to a rapid decrease in Na content for Na-ZSM-5 zeolite. The reaction results indicated that Na-ZSM-5 and H-ZSM-5 with different SiO2/Al2O3 molar ratios all exhibited high activity for methanol conversion. Ammonium exchange and the decreased SiO2/Al2O3 molar ratio of ZSM-5 zeolite led to an increase both in strong acid sites and weak acid sites. Na-ZSM-5 with high SiO2/Al2O3 molar ratio was favorable for the formation of propylene. The highest propylene selectivity (45.9%) was obtained over Na-ZSM-5 zeolite catalyst with SiO2/Al2O3 molar ratio of 220.     

Tuning the base properties of Mg–Al hydrotalcite catalysts using their memory effect

Herein,the relationship between the structure and base properties of Mg–Al hydrotalcite catalysts was comprehensively investigated in relation to heat treatment and rehydration processes,which are well known as memory effects of hydrotalcite.The structure of Mg–Al hydrotalcites changed from layered double hydroxide(LDH)to mixed metal oxide and subsequently to a spinel structure during heat treatment,and it was returned from mixed metal oxide to a LDH structure by rehydration.Based on various characterizations,we successfully proposed a detailed mechanism of memory effect.We also confirmed that the Mg–Al hydrotalcites had weak or strong base sites and that their base properties could be systematically tuned by heat treatment and rehydration.The prepared Mg–Al hydrotalcites were applied to a model reaction,isomerization of glucose to fructose,as base catalysts.Among the catalysts tested,the rehydrated Mg–Al hydrotalcite efficiently produced fructose due to its appropriate base and structure properties.We finally concluded that the base sites of Mg–Al hydrotalcites can be designed as desired by heat treatment and rehydration.Moreover,through systematic design of the base sites of Mg–Al hydrotalcites,these can be promising catalysts for various heterogeneous reactions over base catalysts,giving excellent catalytic performances.     

Effect of Al2O3 Binder on the Precipitated Iron-Based Catalysts for Fischer-Tropsch Synthesis

A series of iron-based Fischer-Tropsch synthesis (FTS) catalysts incorporated with Al2O3 binder were prepared by the combination of co-precipitation and spray drying technology. The catalyst samples were characterized by using N2 physical adsorption, temperature-programmed reduc-tion/desorption (TPR/TPD) and Mossbauer effect spectroscopy (MES) methods. The characterization results indicated that the BET surface area increases with increasing Al2O3 content and passes through a maximum at the Al2O3/Fe ratio of 10/100 (weight basis). After the point, it decreases with further increase in Al2O3 content. The incorporation of AI2O3 binder was found to weaken the surface basicity and suppress the reduction and carburization of iron-based catalysts probably due to the strong K-Al2O3 and Fe-Al2O3 interactions. Furthermore, the H2 adsorption ability of the catalysts is enhanced with increasing Al2O3 content. The FTS performances of the catalysts were tested in a slurry-phase continuously stirred tank reactor (CSTR) under the reaction conditions of 260℃, 1.5 MPa, 1000 h-1 and molar ratio of H2/CO 0.67 for 200 h. The results showed that the addition of small amounts of Al2O3 affects the activity of iron-based catalysts to a little extent. However, with further increase of Al2O3 content, the FTS activity and water gas shift reaction (WGS) activity are decreased severely. The addition of appropriate Al2O3 do not affect the product selectivity, but the catalysts incorporated with large amounts of Al2O3 have higher selectivity for light hydrocarbons and lower selectivity for heavy hydrocarbons.     

Effects of Zr/Ti molar ratio in SO42-/ZrO2-TiO2 calcined at different temperatures on its surface properties and glucose reactivity in near-critical methanol

Effects of Zr/Ti molar ratio in SO42-/ZrO2-TiO2 solid acid catalyst calcined at different temperatures on its surface properties and catalytic activity were thoroughly investigated in this paper. The physicochemical characteristics of prepared samples were determined by N2 adsorptiondesorption, XRD, NH3-TPD and XPS techniques, respectively. It was found that the crystallization temperature of the samples increased after the combination of ZrO2 and TiO2; and phase transformations from the anatase to the rutile of TiO2 species and the tetragonal to the monoclinic of ZrO2 species were effectively suppressed at higher temperature. The sample with a Zr/Ti molar ratio of 3/1 calcined at 450℃ showed the highest surface area and the most acid sites among all the tested samples. The acid site densities of samples were relatively closed to each other if they were calcined at the same temperature, however, decreased with the calcination temperature. The result indicates that the sulfur content in samples is a crucial factor to control the acid site density. Calcining the sample at 650℃ and higher temperatures resulted in a significant desorption of sulfate ion on the samples. The synthesized samples were evaluated as a potential catalyst for glucose conversion under the near-critical methanol conditions (200℃/4 MPa). The results suggested that the relatively weaker acid sites of the catalyst were more favorable for the accumulation of methyl glucosides, while the moderate acid sites were responsible for the formation of methyl levulinate. The catalytic activity for methyl levulinate production almost increases linearly with the catalyst acid site density. The catalyst deactivation is due to the loss of sulfate ion and the two catalysts with Zr/Ti molar ratios of 3/1 and 1/3 could effectively alleviate the deactivation caused by sulfate solution in the reaction medium and can be reused after calcination with the reuse rate of over 90% in terms of the methyl levulinate selectivity.     

A high-surface-area silicoaluminophosphate material rich in Brnsted acid sites as a matrix in catalytic cracking

A transparent gel-like mesoporous silicoaluminophosphate material (SAP) with a Si/Al molar ratio of 20 was synthesized by hydrothermal method. The physicochemical features of SAP were characterized by XRD, XRF, BET, SEM and FT-IR spectroscopy of pyridine adsorption techniques. The results indicated that incorporation of phosphorus (P) into aluminasilica system altered the basic textural characteristics of aluminasilica. Especially after hydrothermal treatment, the material with large special surface area (up to 492 m 2 /g) exhibited a good performance on hydrothermal stability. Moreover, the phosphorus modifier can not only increase the amount of Bro¨nsted acidic sites (up to 48.44 μmol/g) and the percentage of weak acidic sites in total acidic sites, but also regulate the acid type, such as the ratio of B/L (Bro¨nsted acid/Lewis acid) increases to 1.15. The performances of samples as matrices for the catalytic cracking of heavy vacuum gas oil (VGO) were investigated. At 520 C, the catalysts showed much higher gasoline and diesel oil yields achieving to 45.59 wt% and 19.20 wt%, respectively, and lower coke selectivity (2.86%) than conventional FCC matrices, such as kaolin and amorphous silica-alumina.     

CO_2 Reforming of CH_4 over Ni/CeO_2-ZrO_2-Al_2O_3 Prepared by Hydrothermal Synthesis Method

The Ni/CeO2-ZrO2-Al2O3 catalyst with different Al2O3 and NiO contents were prepared by hydrothermal synthesis method. The catalytic performance for CO2 reforming of CH4 reaction, the interaction among components and the relation between Ni content and catalyst surface basicity were investigated. Results show that the interaction between NiO and Al2O3 is stronger than that between NiO and CeO2-ZrO2.The addition of Al2O3 can prevent the formation of large metallic Ni ensembles, increase the dispersion of Ni, and improve catalytic activity, but excess Al2O3 causes the catalyst to deactivate easily. The interaction between NiO and CeO2 results in more facile reduction of surface CeO2. The existence of a small amount of metallic Ni can increase the number of basic sites. As metallic Ni may preferentially reside on the strong basic sites, increasing Ni content can weaken the catalyst basicity.     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

镁铁水滑石的制备及其对小球藻油脂合成生物柴油的催化性能

用改良尿素法制备了镁铁水滑石(MgFe-LDH),对其在小球藻油脂合成生物柴油反应中的催化性能进行了研究。利用XRD、FT-IR、SEM及FT-IR拟合、去卷积分析等技术对所制备的MgFe-LDH进行了表征,考察了pH值、Mg/Fe摩尔比、反应温度和时间对其结构和性能的影响。结果表明,Mg/Fe摩尔比为3或4、pH值为9.5,在110 ℃条件下反应10 h,所制备的MgFe-LDH(Mg3Fe或Mg4Fe)结晶度最高,粒径均匀,结构规整。与Mg/Fe摩尔比为2的MgFe-LDH(Mg2Fe)相比,Mg3Fe或Mg4Fe在完全分解焙烧时,其层板结构保持稳定,具有较高的晶体结晶度、较多的催化活性位和较高的催化活性。以Mg3Fe金属氧化物为催化剂,在醇/油摩尔比为6时反应1.5 h,生物柴油产率可达87％;该催化剂循环使用3次,仍具一定催化活性。     

硝酸镁在γ-Al2O3上的热分解及MgO/γ-Al2O3

研究了不同载量时Mg(NO     

Hydrogen production from simulated hot coke oven gas by catalytic reforming over Ni/Mg(A1)O catalysts

Hydrogen production by catalytic reforming of simulated hot coke oven gas (HCOG) with toluene as a model tar compound was investigated in a fixed bed reactor over Ni/Mg(Al)O catalysts. The catalysts were prepared by a homogeneous precipitation method using urea hydrolysis and characterized by ICP,BET, XRD, TPR, TEM and TG. XRD showed that the hydrotalcite type precursor after calcination formed (Ni,Mg)Al2O4 spinel and Ni-Mg-O solid solution structure. TPR results suggested that the increase in Ni/Mg molar ratio gave rise to the decrease in the reduction temperature of Ni2+ to Ni0 on Ni/Mg(Al)O catalysts. The reaction results indicated that toluene and CH4 could completely be converted to H2 and CO in the catalytic reforming of the simulated HCOG under atmospheric pressure and the amount of H2 in the reaction effluent gas was about 4 times more than that in original HCOG. The catalysts with lower Ni/Mg molar ratio showed better catalytic activity and resistance to ceking, which may become promising catalysts in the catalytic reforming of HCOG.     

Aldol condensation of furfural and acetone on layered double hydroxides

The Aldol condensation of furfural (Fur) with acetone (Ac) to 4-(2-Furyl)-3-buten-2-one (FAc) is one of the most important processes in the aqueous-reforming of oxygen-containing biomass derivatives and has been carried out in the presence of solid-base catalysts, calcined-rehydrated Layered Double Hydroxides (LDH). The Mg-Al Layered Double Hydroxides has been prepared by the coprecipitation, calcination and regeneration from mixed oxides by rehydration. The catalyst prepared with different Mg/Al molar ratios showed different catalytic performance and the best catalyst was with the Mg/Al molar ratio of 2.5. Phenol adsorption showed that the best catalyst had the largest numbers of accessible basic sites. The appropriate rehydration temperature and time for mixed oxides obtained by calcination were also investigated. The Mg-Al LDH catalysts can be regenerated by calcination at 773 K and rehydration in decarbonate water, but the regeneration is complex and incomplete. In addition, the catalyst calcined at high temperature also had activity, which was attributed to the formation of the Mg-Al spinels.     

Fourier transform infrared study of low-temperature CO adsorption on CuMgAl-hydrotalcite

Single-phase CuMgAl ternary hydrotalcite with (Cu+Mg)/Al atomic ratio of 3.0 and Cu/Mg atomic ratio of 1.0 was synthesized by coprecipitation. Thermoanalytical studies of this sample showed transformations in three stages in the temperature range up to ca. 900 K yielding mainly CuO phase. In situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopic measurements showed the presence of carbonates even after calcination of the sample at 973 K. The genesis of Cu+ sites during thermal treatment in vacuo at different temperatures for this sample was followed by IR spectroscopy of CO adsorbed at low temperature. Essentially no Cu+ sites are present on a sample calcined at 723 K, consistent with X-ray photoelectron spectroscopic (XPS) data. However, sample subjected to activation (1 h of O2 treatment at 723 K followed by 1 h of evacuation at the same temperature) upon CO adsorption at 85 K unambiguously showed the presence of Cu+ sites. 12CO-13CO coadsorption studies confirmed the presence of dicarbonyls, which are converted to linear Cu+-CO species during evacuation at 85 K. Concentration of the accessible Cu+ sites increased with the increase in activation temperature up to 873 K and decreased with a further temperature rise. The copper sites on the sample are heterogeneously distributed and their distribution depends on the activation temperature. Two routes of reduction of Cu2+ to Cu+ are proposed: (i) autoreduction during evacuation and (ii) reduction by CO.     

Preparation of supported metal catalysts starting from hydrotalcites as the precursors and their improvements by adopting “memory effect”

Hydrotalcite-like compounds (HTlcs) can be used as the catalysts as it is since they contain various transition metal cations as the catalytically active species well dispersed on the basic support materials. Moreover, increasing numbers of the applications of HTlcs after the heat treatment have been found since the oxides with very small crystal size, stable to thermal treatments, are obtained after the calcination. The oxides possess interesting properties such as high surface area, basic properties and further form small and thermally stable metal crystallites by reduction. Moreover, the calcined oxides show a unique property, i.e., “memory effect,” which allows the reconstitution of the original hydrotalcite structure. We have developed the catalytic applications of hydrotalcites as it is and moreover the mixed oxides derived from hydrotalcites for various catalytic reactions, i.e., oxidation, dehydrogenation and reforming of hydrocarbons, and even for the reforming of methanol and the CO shift reaction. Aerobic oxidation of alcohols, Baeyer−Villiger oxidation of ketones and O₃ oxidation of oxalic acid have been successfully carried out with the Mg−Al hydrotalcites containing Ni, Fe and Cu, respectively, as the catalysts in liquid phase. In the O₃ oxidation of oxalic acid, the catalytic activity was enhanced by the “memory effect,” i.e., Mg(Cu)–Al hydrotaclite was reconstituted on the surface of Mg(Cu,Al)O periclase particles and oxalic acid was incorporated as anions in the hydrotalcite layer, resulting in an enhanced oxidation of oxalic acid. As the catalysts in the vapor phase reactions, Mg/Fe/Al mixed oxides prepared from Mg–Al(Fe) hydrotalcites and effectively catalyzed the dehydrogenation of ethylbenzene. Supported Ni metal catalysts have been prepared from Mg(Ni)–Al hydrotalcites and successfully used in the steam reforming and the oxidative reforming of methane and propane. Moreover, the Ni catalysts have been improved by combining a trace amount of noble metals by adopting the “memory effect” and used in the production of hydrogen for the PEFC under the daily startup and shutdown operation. Also starting from aurichalcite or hydrotalcite precursor as the precursor, Cu/Zn/Al catalysts with high Cu metal surface area have been prepared and successfully applied in the steam reforming of methanol and dimethyl ether, and moreover in the CO shift reaction.     

Cu(Al)O复合物表面酸碱性质的微量吸附量热研究

673K分解Cu/AI物质的量比分别为0．5、1和2的Cu-AI水滑石转化为Cu(AI)O复合物。XRD测定仅显示CuO物相,表明组成成分较均一。微量吸附量热法测定Cu(AI)O复合物表面酸碱中心的强度和数量,给出了吸附分子CO2／NH3的吸附曲线。量热结果展示,样品的酸中心强度顺序是：0．5CAO＞CAO＞2CAO,而碱中心强度顺序是：0．5CAO＜CAO＜2CAO。显然,样品的酸性（碱性）随着AI(Cu)含量的提高而逐渐增强。研究表明,样品的NH3和CO2起始吸附热与其Sanderson电负性线性相关。     

Hydrogen production from simulated hot coke oven gas by catalytic reforming over Ni/Mg（Al）O catalysts

Hydrogen production by catalytic reforming of simulated hot coke oven gas (HCOG) with toluene as a model tar compound was investigated in a fixed bed reactor over Ni/Mg(Al)O catalysts. The catalysts were prepared by a homogeneous precipitation method using urea hydrolysis and characterized by ICP, BET, XRD, TPR, TEM and TG. XRD showed that the hydrotalcite type precursor after calcination formed (Ni, Mg)Al₂O₄ spinel and Ni-Mg-O solid solution structure. TPR results suggested that the increase in Ni/Mg molar ratio gave rise to the decrease in the reduction temperature of Ni²⁺ to Ni⁰ on Ni/Mg(Al)O catalysts. The reaction results indicated that toluene and CH₄ could completely be converted to H₂ and CO in the catalytic reforming of the simulated HCOG under atmospheric pressure and the amount of H₂ in the reaction effluent gas was about 4 times more than that in original HCOG. The catalysts with lower Ni/Mg molar ratio showed better catalytic activity and resistance to coking, which may become promising catalysts in the catalytic reforming of HCOG.