Effect of cobalt loading on reducibility, dispersion and crystallite size of Co／Al2O3 Fischer-Tropsch catalyst

Co/Al2O3 Fischer-Tropsch synthesis catalysts with different cobalt loadings were prepared using incipient wetness impregnation method. The effects of cobalt loading on the properties of catalysts were studied by means of X-ray diffraction (XRD), temperature programmed reduction (TPR), hydrogen temperature programmed desorption (H2-TPD) and O2 titration. Co-support compound formation can be detected in catalyst system by XRD.For the Co/Al2O3 catalysts with low cobalt loading, CoAl2O3 phase appears visibly. Two different reduction regions can be presented for Co/Al2O3 catalysts, which belong to Co3 O4 crystallites (reduction at 320 ““C) and cobalt oxidealumina interaction species (reduction at above 400℃). Increasing Co loading results in the increase of Co3 O4 crystallite size. The reduced Co/Al2O3 catalysts have two adsorption sites, and cobalt loading greatly influences the adsorption behavior. With the increase of cobalt loading, the amount of low temperature adsorption is increased, the amount of high temperature adsorption is decreased, and the percentage reduction and cobalt crystallite size are increased.     

Preparation, characterization and photocatalytic behavior of WO3-TiO2/Nb2O5 catalysts

TiO2/Nb2O5 photocatalyst loaded with WO3 (WO3-TiO2/Nb2O5) was prepared by a modified hydrolysis process, and characterized by X-ray diffractometry, transmission electron microscopy, Raman spectra and UV-Vis diffuse refraction spectroscopy. The photocatalytic activity of WO3-TiO2/Nb2O5 was investigated by employing splitting of water for O2 evolution. The results indicate that WO3 loading can pronouncedly improve the photocatalytic activity of TiO2/Nb2O5 by using Fe3 as an electron acceptor under UV irradiation. The optimum molar fraction of the loaded WO3 is 2%, and the largest speed of O2 evolution for 2% WO3-TiO2/Nb2O5 catalyst is 151.8 μmol/(L·h).     

Facile Synthesis of 2PbCO3·Pb(OH)2 Microcrystals and Its Catalytic Behavior for Transesterification of Dimethyl Carbonate with Phenol

Polyhedron lead hydroxide carbonate （2PbCO3·Pb（OH）2 ） microcrystals have been prepared in solution phase via a facile method in the presence of surfactant cetyltrimethylammonium bromide （CTAB）. All the samples were characterized by powder X-ray diffraction ,pattern （XRD）, field-emission scanning electron mi- croscopy （FE-SEM）, high-resolution transmission electron microscopy （HRTEM）, and selected area electron diffraction （SAED）. The possible growth mechanism was discussed. 2PbCO3·Pb（OH）2 microcrystals were found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate （DPC） by transesterification of dimethyl carbonate （DMC） with phenol. Compared with some other catalysts, such as AlCl3, ZnCl2, and Mg5（CO3）4（OH）2, 2PbCO3·Pb（OH）2 microcrystals are stable and show relatively high activity at low catalyst amount. When the reaction was carried out at 180 12, with a molar ratio of phenol to DMC of 2：1, a reaction time 14 h, and a catalyst amount 0.2% （molar ratio to phenol）, the selectivity of DPC and methyl phenyl carbonate （MPC） was 14.7% and 78.8%, respectively.     

Use of lime mud from paper mill as a heterogeneous catalyst for transesterification

Lime mud(LM),a solid waste from the paper mill,is used as an economic and environmental friendly heterogeneous basic catalyst for transesterification,which is accompanied by characterization of X-ray fluorescence,thermogravimetric-differential thermal analysis,X-ray diffraction,N2adsorption,and Hammett indicator method.To investigate the performance of the achieved catalyst,which is activated through calcination,the aspects of calcination temperature,reaction time,mole ratio of methanol to oil,catalyst addition percentage,and reaction temperature are concerned.Characterization of catalyst reveals that LM could be activated through calcination to transform the carbonate and hydrate of calcium into the oxide forms and higher calcination temperature could lead to stronger basic strength.However,N2adsorption results indicate that higher temperature causes the sintering of the catalyst and shrinkage of the catalyst grains.When LM is activated at 800°C(LM-800)and the reaction is carried out at 64°C with a methanol to oil mole ratio of 15:1,catalyst addition percentage of 6%,and reaction time of 2h,the maximum transesterification conversion of 94.35%could be achieved.Reusability of LM-800 is also investigated compared with laboratory grade CaO in five reaction cycles and the results indicate that the catalysts derived from LM can be used as an economic and efficient catalyst for biodiesel production.     

Investigation on preparation of CuO-SnO2 -CeO2γ-Al2O3 catalysts for catalytic wet air oxidation process and their catalytic activity for degradation of phenol

Catalytic Wet Air Oxidation process is an efficient measure for treatment of wastewater with great strength which is not biodegradable. Heterocatalysts now become the key investigation subject of catalytic wet air oxidation process due to their good stability and easy separation. In the paper, CuO-SnO2-CeO2/γ-Al2O3 catalysts are prepared by impregnation method, with SnO2 as a doping component, CuO as an active component, CeO2 as a structure stabilizer, γ-Al2O3 as a substrate. XPS test is carried out to investigate the effect of Sn on the chemical surrounding of Cu and O element on the catalyst surface and their catalytic activity. It is shown that the right doping of Sn can increase Cu content on the catalyst surface, as a result the quantity of adsorption oxygen is also increased. It is found that Cu content on the catalyst surface is one of the primary factors that determin catalytic activity of catalyst through analyzing the catalytic wet air oxidation process of phenol.     

Decoioration and mineralization of yeast wastewater by using Ce-Fe/Al2O3 as heterogeneous photo-Fenton catalyst

Decoloration and mineralization of yeast wastewater were investigated by using Ce-Fe/Al2O3 as a heterogeneous photo-Fenton catalyst in fluidized bed reactor in order to solve the problem of yeast wastewater discharge. The experimental results were assessed in terms of total organic carbon（TOC） reduction. The operational and reaction conditions affecting the efficiencies of TOC removal such as initial pH value, H2O2 concentration, catalyst loading and UV power were studied. The results show that TOC is reduced from 347.6 mg/L to 10.8 mg/L, color is changed from 500 units to 0 under the conditions as follows： initial pH value 6. 0, H2O2 concentration of 1. 000 g/L, catalyst loading of 5 g/L, reaction duration of 120 rain and reaction temperature of 30 ℃. The irradiated Ce-Fe/Al2O3 catalyst was complexed with 1,10-phenanthroline and then it was subjected to Fourier transform infrared spectroscopy and diffuse reflectance spectroscopy to confirm the formation of Fe（Ⅱ） in the solid state. Heterogeneous photo-Fenton reaction proves to be effective for the treatment of yeast wastewater.     

Polyoxometalates Pillared Hydrotalcite： Synthesis and Catalysis in Transesterification of Dimethyl Carbonate and Phenol

The salts of para-tungstic and para-molybdic were heterogenized for their effective use as solid catalysts in the transesterification reaction of dimethyl carbonate and phenol by inserting them between the layers of Mg₂Al-hydrotalcite. These catalysts were characterized by FT-IR spectra and X-ray powder diffraction. Polyoxometalates (POMs) clusters were intercalated into the interlayer of layered double hydroxide (LDH) via anion exchange with organic acid precursor in Mg₂Al-LDH, and the integrity of the clusters ^6- and ^6- was maintained. The intercalated para-molybdic cluster showed high catalytic activity and reusability in the transesterification under mild reaction conditions. When the reaction was carried out at 180?℃, with a molar ratio of phenol to DMC of 1∶1, a reaction time 10?h, and a catalyst amount 1%(wt), the conversion of phenol was 10.0%, the selectivities of diphenyl carbonate and methyl phenyl carbonate were 10.7% and 86.1%, respectively.     

Sulfur poisoning mechanism of three way catalytic converter and its grey relational analysis

Combining a detailed catalytic surface reaction mechanism with noble metal and promoter elementary reactions, a new three-way catalytic converter（TWC） reaction mechanism is established. Based on the new mechanism, steady condition numerical simulation is carried out, and the change of light-off temperatures and conversion efficiency with various SO2 contents is obtained. By grey relational analysis（GRA）, the relational grade between conversion efficiency and SO2 content is obtained. And, the result shows that SO2 content has the most important influence on C3H6 and NOX conversion efficiency. This provides an important reference to the improvement of activity design of TWC, and may provide guidance for the condition design and optimization of TWC.     

Activity model and its application in CaO-FeO-SiO2-MoO3 quarternary system

The activity model of CaO-FeO-SiO2-MoO3 quarternary system was established according to the coexistence theory of slag structure and the reduction thermodynamics of molybdenum oxide was discussed by applying this model. The activities of SiO2 and MoO3 decrease, while that of CaO increases with increasing the basicity of slag. Among SiC, [C] and [Si] reactants, the reducing capability of SiC is the strongest, while that of [C] is the poorest at a high temperature (about 1873 K). It is advantageous to increase the yield of molybdenum by increasing the content of [Si] or [C]. Controlling of basicity of slag can prevent the oxidation loss of molybdenum.     

Synthesis,characterization and catalytic application of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/MCM-48 in the esterification of methacrylic acid with n-butyl alcohol

A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H3PW12O40/MCM-48 is an excellent catalyst for synthesizing n-butyl methacrylate and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）：n（n-butyl alcohol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.6, mass ratio of catalyst used to the reactants is 0.5% and reaction time is 2.0 h. Under these conditions, the yield of n-butyl methacrylate can reach 93.7%.     

Photocatalytic oxidation of Rhodamine B in a three-phase internal circulating fluidized bed with TiO2/SiO2 as photocatalyst

A novel photoreactor of three-phase internal circulating fluidized bed was applied to the degradation of Rhodamine B with TiO2/SiO2 catalyst and TiO2 powder,respectively.The experimental results showed that the photocatalytic activity of TiO2/SiO2 catalyst was much higher than that of TiO2 powder under the same condition,and the half life of Rhodamine B using TiO2/SiO2 was 9.5 min,much lower than 63 min when using TiO2 powder.Moreover,TiO2/SiO2 had a good adsorption capacity of Rhodamine B,which played an important role on degradation.In addition,it was found that the degradation kinetics of Rodamine B with TiO2/SiO2 catalyst did not follow the first order reaction.The degradation kinetics model in terms of the adsorption process of catalyst and the analytic solution of reactant degradation rate in liquid phase could be deduced,which consisted of two parts.The first part was due to the adsorption,while the second part was due to the photocatalysis.In the beginning of the reaction,the adsorption process was dominant.However,when the adsorption achieved a balance,the degradation of Rhodamine B in liquid phase and solid phase was mainly caused by photocatalysis and the degradation kinetics model conformed to the first order reaction.     

New technique of comprehensive utilization of spent Al2O3 -based catalyst

A new technology was developed to recover multiple valuable elements from the spent Al2O3-based catalyst by X-ray phase analysis and exploratory experiments. The experimental results show that in the condition of roasting temperature of 750 ℃ and roasting time of 30 min, molar ratio of Na2O to Al2O3 of 1.2, the leaching rates of alumina, vanadium and molybdenum in the spent catalyst are 97.2%, 95.8% and 98.9%, respectively. Vanadium and molybdenum in sodium aluminate solution can be recovered by precipitators A and B, and the precipitation rates of vanadium and molybdenum are 94. 8% and 92. 6%. Al（OH）3 was prepared from sodium aluminate solution in the carbonation decomposition process, and the purity of Al2O3 is 99. 9% after calcination, the recovery of alumina reaches 90. 6% in the whole process; the Ni-Co concentrate was leached by sulfuric acid, a nickel recovery of 98. 2% and cobalt recovery over 98.5% can be obtained under the experimental condition of 30% H2SO4, 80 ℃, reaction time 4 h, mass ratio of liquid to solid 8, stirring rate 800 r/min.     

Synthesis and performance of mesoporous phosphotungstic acid/alumina composite as a novel oxidative desulfurization catalyst

A series of mesoporous phosphotungstic acid/alumina composites （HPW/Al_2O_3） with various HPW contents were synthesized by evaporation-induced self-assembly method. These composites were characterized by nitrogen adsorption-desorption, TEM, FTIR, and UV-vis, and were tested as catalysts in oxidation desulfurization of model fuel composed of dibenzothiophene （DBT） and hydrocarbon, using H202 as the oxidant. These composites exhibited high activity in catalytic oxidation of DBT in model fuel and good reusing ability. The best performance was achieved by using the mesoporous HPW/Al_2O_3 with 15wt% HPW content, which resulted in a DBT conversion of 98% after 2 h reaction at 343 K, and it did not show significant activity degradation after 3 recycles. Characterization results showed that the mesoporous structure of alumina and the Keggin structure of HPW were preserved in the formed composite. These results suggested that HPW/ Al_2O_3 could be a promising catalyst in oxidative desulfurization process.     

Degradation of n-butyl xanthate using fly ash as heterogeneous Fenton-like catalyst

Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investigated. The fly ash/H2O2 catalyst possesses a high oxidation activity for n-butyl xanthate degradation in aqueous solution. It is found that both the dosage of catalyst and initial solution pH significantly affect the n-butyl xanthate conversion efficient. The results indicate that by using 1.176 mmol/L H2O2 and 1.0 g/L fly ash catalyst with mass fraction of 4.14% Fe（III） oxide at pH 3.0, almost 96.90% n-butyl xanthate conversion and over 96.66% COD removal can be achieved within 120 min with heterogeneous catalysis by fly ash. CS2 as an intermediate of n-butyl xanthate oxidation. Finally, it is demonstrated that the fly ash/H2O2 catalytic oxidation process can be an efficient method for the treatment of n-butyl xanthate containing wastewater.     

In Situ Growth of Vanadium Oxide on Reduced Graphene Oxide for the Low-Temperature NO-SCR by NH_3

The vanadium oxide/reduced graphene oxide(V_2 O_5/rGO) composite catalyst which determined the selective catalytic reduction activity(SCR) of NO with NH_3 was prepared by a simple solvothermal method. The physicochemical properties of the catalysts were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), Raman, X-ray energy spectrometer(XPS) and N_2 sorption isotherm measurement(BET). Results of NH_3-SCR showed that the NO conversion of V_2 O_5/rGO catalyst could reach 54.3% at 100 ℃. And the removal of NO increased to 74.6% when the temperature was up to 220 ℃. By characterizing the microstructure and morphology of the V_2 O_5/rGO catalysts prepared by in-situ growth and mechanical mixing methods, it was further shown that V_2 O_5 nanoparticles were highly dispersed and in situ growth on the rGO surface. Based on X-ray energy spectrometer, V_2 O_5/r GO catalyst had good low temperature denitrification performance due to the chemical adsorption oxygen and low-valent vanadium oxide contained in V_2 O_5/rGO catalyst, which was beneficial to the redox reaction between V_2 O_5 and graphene.     

Preparation,characterization of superacid SO4 2−/ZrO2-SiO2 and its activity on catalytic synthesis of methyl p-nitrobenzoate

Solid superacid SO42-/Zr O2-SiO2 was prepared by dip-impregnation method, and its catalytic activity was tested with esterification of p-nitrobenzoic acid and methanol. The optimum conditions were also found, that is, the molar ratio between silica and zirconia was 10:1, the calcination temperature was 550 ℃ and the soaked consistency of H2SO4 was 1.0 mol?L-1. Under the conditions that the ratio of methanol to acid(m L/g) was 12:1, the amount of catalyst was 0.5 g, the reaction time was 5 h and the stirring speed was 800 r?min-1, the yield of methyl p-nitrobenzoate could reach up to 90.5%. Then the characterizations of cataslyst, including the acidity and types of acidic centers, specific surface area and surface structure was respectively examined by Hammett indicator, in-situ pyridine IR, BET method, FT-IR(KBr), transmission electron microscope(TEM), and X-ray diffraction(XRD). The results showed that the catalyst SO42-/Zr O2-SiO2 was superacid with high specific surface area due to Ho-12.70. It contained acidic sites of Lewis and BrΦnsted, and its surface structure changed after esterification. The zirconia crystal was mainly tetragonal and silica crystal was not found.     

Preparation and characterization of Cu-doped mesoporous CeO2for CO oxidation简

Mesoporous CeO2 was first synthesized by hydrothermal method,and then used to synthesize different contents of CuO）x/CeO2（x：molar ratio of Cu to Ce） by deposition-precipitation method.These materials were characterized by X-ray diffraction（XRD）,N2 adsorption and desorption,H2 temperature programmed reduction（H2-TPR） and O2 temperature programmed desorption（O2-TPD） to study the crystal structure,surface area,and the mechanism of CO oxidation.The results show that,on XRD patterns,no evidence of CuO diffraction peaks is present until Cu loading is increased to 20%.The BET surface area decreases noticeably with the increase of Cu content.Compared with other samples,the better reducibility and activity oxygen species of（CuO）10%/CeO2coincide with its better catalytic activity.     

Catalysis of Active Carbon Supporting Transition Metal Oxides for Pyrotechnical Reagent with Potassium Perchlorate

In order to improve the pyrotechnical reagent with potassium perchlorate,composite catalyst of active carbon supporting transition metal oxides (TMO),Fe2O3 and CuO,were prepared and added into pyrotechnical reagent with potassium perchlorate.Accelerating rate calorimeter (ARC) was used to study the catalysis of pyrotechnical reagent which is consisted of potassium perchlorate and composite catalyst.Composite catalyst of both Fe2O3 and CuO supported by active carbon can catalyze pyrotechnical reagent with potassium perchlorate.Furthermore,it can lower the apparent activation energy and accelerate the reaction with a smaller quantity than that with Fe2O3 and CuO.The maximal reaction rate of pyrotechnical reagent with potassium perchlorate mixed with Fe2O3/active carbon and CuO/active carbon is 8.31 min-1 and 9.13 min-1,which is 1.74 times and 1.91 times of pyrotechnical reagent mixed with no catalyst;time to maximal rate was 18.99 min and 1.96 min respectively,which is lower than pyrotechnical reagent mixed with no catalyst by 86.46% and 98.67% ;the apparent activation energy is 368.10 kJ·mol-1 and 325.29 kJ·mol-1,which is lower than pyrotechnical reagent mixed with no catalyst by 31.89% and 39.81% respectively.     

Hydrothermally Synthesizing Nanospheres of Pd Loaded TiO_2 for Photocatalytically Reducing CO_2 in Isopropanol to Isopropyl Formate

Photocatalytic reduction of CO_2 was carried out on villiform spherical catalysts of Pd-TiO_2 in isopropanol solution.The catalysts were synthesized by hydrothermal method,their structures,morphologies and optical absorption properties were characterized by X-ray diffraction(XRD),energy dispersive X-ray spectroscopy(EDS),scanning electron microscopy(SEM),transmission electron microscopy(TEM),highresolution transmission electron microscopy(HRTEM)and UV-vis absorption spectroscopy(UV-vis).The photocatalytic activities with different loading amounts and morphologies were evaluated for determining the dominant effect and optimizing the catalyst preparation.Based on a villiform spherical TiO_2 with the largest specific surface area in our experiments,we prepared a set of catalysts with various loading amounts of palladium and tested them by bubbling CO_2 through the slurry of catalyst and isopropanol.The highest formation rate of isopropyl formate was 276.6μmol/g?cat/h.Eventually we proposed the reaction mechanism.     

Preparation of cyclodextrin-based carbonaceous catalyst and its application in the esterification

A new carbonaceous catalyst with sulfonic acid group (-SO3H) was prepared by incomplete carbonization of β-cyclodextrin followed by sulfonation.The sulfonated amorphous carbon was characterized by IR,elemental analysis,DSC-TGA and PXRD,and the catalytic activity was investigated to be an efficient catalyst for the esterification reactions with maximum yield of 87%.The sulfonated carbonaceous catalyst was readily separated from the reaction solution and keeps approximately equal catalytic activity.The results confirm that the active centre is the hydrophilic sulfonic acid functional group in the esterification reactions.