Promoted catalytic performances of highly dispersed V-doped SBA-16 catalysts for oxidative dehydrogenation of ethane to ethylene

V-doped SBA-16 catalysts (V-SBA-16) with 3D nanocage mesopores have been successfully synthesized by a modified one-pot method under weak acid condition. The obtained materials were characterized by means of small angle XRD, N2adsorption–desorption, TEM, UV–Vis and UV-Raman spectroscopy. These characterization results indicated that well-order mesoporous structures were maintained even at higher vanadium loadings and high concentration of VOxspecies were incorporated into the framework of SBA-16 support. The catalytic performances of V-SBA-16, V/SBA-16 and V/SiO2catalysts were comparatively investigated for the oxidative dehydrogenation of ethane to ethylene. The highest selectivity to ethylene of 63.3% and ethylene yield of 25.6% were obtained over 1.0V-SBA-16 catalyst. The superior catalytic performance of V-SBA-16 catalysts could be attributed to the presence of isolated framework VOxspecies, the unique structure of SBA-16 support and weak acidity. Moreover, V/SiO2catalyst exhibited relatively poor catalytic activity duo to the formation of V2O5nanoparticles on the surface of SiO2support and the low dispersion of VOxspecies. These results indicated that the catalytic performances of the studied catalysts were strongly dependent on the vanadium loading, the nature and neighboring environment of VOxspecies and the structure of support. © 2016

Fischer–Tropsch synthesis on impregnated cobalt-based catalysts:New insights into the effect of impregnation solutions and pH value

The Co-based catalysts were prepared with different cobalt acetate solutions. Effects of pH value were studied deeply on Fischer–Tropsch synthesis (FTS) through a semi-batch reactor. Among all impregnation solutions (water, butanol, amyl alcohol, acetic acid, nitric acid and ammonium nitrate), the catalyst prepared by NH4NO3solution showed the highest catalytic activity due to its small particle size and high reduction degree. However, the catalyst with the smallest particle size derived from water as impregnation solution exhibited low activity as well as high methane selectivity since it was difficult to be reduced and inactive in FTS. According to FT-IR spectra results, the low intensity of absorbed CO on the catalyst prepared from water solution resulted in low FTS activity. Whereas, the high activity of catalysts prepared from NH4NO3solution could be explained by the high intensity of absorbed CO on the catalysts. The cobalt species on the catalysts prepared under lower pH conditions exhibited smaller particle size distribution as well as lower CO conversion than those prepared at higher pH value. © 2016 Science Press

Regeneration of waste SCR catalyst by air lift loop reactor

A solution of 0.1 mol/L to 1.0 mol/L H2SO4 can dissolve alkali metals and alkaline earth metals which weaken an active site of SCR catalyst. The waste catalyst washed with 0.5 mol/L H2SO4 regained the best catalytic activity. When a concentration of the sulfuric acid is less than 0.5 mol/L, sufficient cleaning effects cannot be obtained. In contrast, when the concentration is greater than 1.0 tool/L, the active components, vanadium and tungsten are undesirably eluted. The total BET surface of the catalyst regenerated by air lift loop reactor showed almost the same as that of fresh catalyst due to the removal of insoluble compounds which may be penetrated into pores of catalyst. The addition of a solution of 0.075 mol/L ammonium vanadate （NHnVO3） and 0.075 mol/L ammonium paratungstate （5（NH4）20· 12WO3-5H20） to 0.1 mol/L H2SO4 significantly increases the activity of the waste catalyst.

Hydrocarbon production rates in Fischer-Tropsch synthesis over a Fe/Cu/La/Si catalyst

The detailed kinetics of Fischer-Tropsch synthesis over an industrial Fe/Cu/La/Si catalyst was studied in a continuous spinning basket re- actor under the conditions relevant to industrial operations. Reaction rate equations were derived on the basis of Langmuir-Hinshelwood- Hougen-Watson type models for Fischer-Tropsch synthesis based on possible reactions sets originated from the carbide, enolic and combined enol/carbide mechanisms. Kinetic model candidates were evaluated by the global optimization of kinetic parameters, which were realized by first minimization of multi-response objective functions with conventional Levenberg-Marquardt method. It was found that an enolic mech- anism based model could produce a good fit of the experimental data. The activation energy for paraffin formation is 95 kJ.mo1-1 which is smaller than that for olefin formation （121 kJ.mol-1）.

Effect of Ammonia on the Performance of Catalysts for Selective Hydrogenation of 1-Methylnaphthalene

The effect of ammonia on the catalytic performance for 1-methylnaphthalene(1-MN) selective hydrogenation saturation was studied with Co-Mo/γ-Al_2O_3, Ni-W/γ-Al_2O_3, Ni-Mo/γ-Al_2O_3, and Ni-Mo-W/γ-Al_2O_3 catalysts. The results indicated that Ni-Mo-W/γ-Al_2O_3 catalyst exhibited the best performance for saturation of 1-MN. The introduction of NH3 remarkably inhibited the hydrogenation of 1-MN in the dynamic control area, but it had no effect in the thermodynamic control area. Besides, the mono-aromatics selectivity on the Ni-Mo-W and Ni-Mo catalysts was enhanced. However, it had little effect on the Ni-W and Co-Mo catalysts.

Research progress in the SO2 resistance of the catalysts for selective catalytic reduction of NOx

The selective catalytic reduction （SCR） of NOx with NH3 has been proven to be an efficient technology for NOx conversion to N2. However, the catalysts used for SCR usually suffer from the problem of sulfur poisoning which seriously limits their practical application. This review summarized sulfur poisoning mechanisms of various SCR deNG catalysts and strategies to reduce deactivation caused by SO2 such as doping metals, controlling the structures and morphologies of the catalysts, and selecting appropriate supports. The methods and procedures of catalysts preparation and the reaction conditions also have effect on SO2-resistance of the catalysts. Several novel catalyst systems that exhibited good SO2 resistance are also introduced. This paper could provide guidance for the development of highly efficient sulfur-tolerant deNOx catalysts.

3D Simulation Research on Urea-SCR DeNO_x Catalyst for Diesel Engine

In order to reduce oxides of nitrogen （NOx） emanated from a diesel engine, a comprehensive urea selective catalyst reduction （SCR） DeNOx catalyst was modeled in which numerical simulations were used as a complementary tool for the experimental investigations to make the design decisions, and hence shorten the de- velopment process. In this approach, relevant conversion reactions were studied in 1D model, and the parame- ters obtained in this way were transferred to 3D simulations. According to the results of the study, the conver- sion of NO and NO2 increased with the increase in monolith solid temperature. With the increase in the ratio of NO2/NOx the conversion of NO, NO2 and NOx increased resulting in maximum reduction of NOxat the ratio of 1; beyond this ratio, the conversion of NO2 and NOx decreased; however, NO continued to be converted till the ratio was 1.8. The conversion of NOx decreased with the increase in space velocity.

EFFECT OF ELECTRON DONORS ON THE SELECTIVE HYDROGENATION OF DIENE TO MONOENE OVER HETEROGENIZED Pd CATALYST

In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron donors can decrease or even cease the monoene hydrogenation and thereby keep the high monoene selectivity after reaching its maximum.

One-step hydrothermal synthesis of Cu-SAPO-34/cordierite and its catalytic performance on NO_x removal from diesel vehicles

Cu-SAPO-34/cordierite catalysts were prepared via one-step hydrothermal synthesis method and their performances to remove NO x from the diesel vehicle exhaust were evaluated. The morphology, structure, Cu content and valence state were characterized by SEM, XRD, ICP and XPS, respectively. The experimental results show the active component Cu of the catalysts via in situ synthesis could significantly improve the selective catalytic reduction （SCR） activities of NOx and the optimal Cu content is in the range of 0.30%-0.40%（mass fraction）. No N 2 O is detected by gas chromatograph （GC） during the evaluation process, which implies that NOx is almost entirely converted to N2 over Cu-SAPO-34/cordierite catalyst. The conversion rate of NOx to N2 by NH3 over catalyst could almost be up to 100%in the temperature range of 300-670 ℃with a space velocity of 12000 h-1 and it is still more than 60% at 300-620 ℃ under 36000 h-1. The catalysts also show the good hydrothermal and chemical stability at the atmosphere with H 2 O.

碳化镍钼催化剂的制备及其甲烷干气重整活性(英文)

Nickel molybdenum carbide catalysts were prepared and their activities in the CO2 reforming of methane at a low CO2/CH4 reactant ratio were investigated using a microreactor at atmospheric pressure and at 973 K.The effect of the catalyst preparation method and the Ni/Mo ratio on the increase in catalyst life and the promotion of catalytic activity were investigated using N2 adsorption,X-ray diffraction, temperature-programmed carburization,temperature-programmed reaction,and a reforming reaction.The 25Ni75Mo catalyst that was carburized at 813 K exhibited the highest hydrogen formation ability and gave the least carbon deposition.The incomplete carburization of the Mo oxide species in the catalyst that was carburized at a lower temperature gradually gave a more active carburized species.The NiMoOxCy in the catalyst was more active in hydrogen formation during the dry reforming of methane whileβ-Mo2C andη-Mo3C2 were less active.

Performance of Methanol-to-Olefins Catalytic Reactions by the Addition of PEG in the Synthesis of SAPO-34

SAPO-34, a silicoaluminophosphate zeolite, has been synthesized by the hydrothermal method with the addition of different molecular weights of polyethylene glycol (PEG), and has been characterized with XRD, SEM, N2adsorption–desorption, FT-IR, and NH3temperature-programmed desorption (NH3-TPD). We studied SAPO-34 as a catalyst in the methanol-to-olefins (MTO) reaction, in a fixed-bed reactor. The results show that the chain length of PEG has a great influence on the particle size and morphology of SAPO-34. PEG acts as inhibitor in the crystallization process. With the increase of the chain length of PEG used in the synthesis, from a relative molecular weight of 400–6000, the morphology of SAPO-34 changes gradually from cubic to nanoplate-like and then changes to cubic again. The particle size decreases markedly at first and then increases to some extent. The catalytic stability in the MTO reaction also increases first and then decreases, with all the catalysts having almost the same selectivity to olefins. When the sample is synthesized with PEG800, the particles become nanoplate-like with a thickness of 46 nm on average, and the catalytic stability is appreciably prolonged, which is attributed to the shorter diffusion paths of the reactants in the zeolite. © 2017 The Author(s)

POLYMORPH CONTROL OF ANTIMONY WHITE(Sb_2O_3)PREPARED BY HYDROMETALLURGY METHOD

The effects of reaction solvent, the properties of Sb 4O 5Cl 2 material and the ligand additives on the reaction rate and polymorph of antimony white(Sb 2O 3) in the reaction of Sb 4O 5Cl 2 transforming into Sb 2O 3 have been investigated by XRD and IR method. It is revealed that the reaction solvent and the properties of Sb 4O 5Cl 2 are the key factors affecting the reaction rate. The polymorph of antimony trioxides is determined by the reaction mechanism, i.e. the coordination state of the antimony activated complex. Adding a little ligand such as EDTA is the most economical and effective method of synthesizing cubic antimony white(Sb 2O 3)in hydrometallurgical transformation process.

Thioetherification of isoprene and butanethiol on transition metal phosphides

Thioetherification between mercaptan and diolefin is an efficient process to remove mercaptans in FCC gasoline at mild condition, during which the selective hydrogenation of diolefin to monoolefin is also expected. Here, Si O2 supported transition metal（Fe, Co, Ni, Mo and W） phosphides were tested for the thioetherification of isoprene and butanethiol on a fixed-bed reactor at 120℃ and 1.5 MPa H2, and their structure before and after reaction was characterized by means of XRD, HRTEM, N2 sorption, CO chemisorption, NH3-TPD, XPS and TG. It was found that, among different metal phosphides, Mo P/Si O2 showed the best performance, and the optimal nominal Mo P loading was 25%. Apart from the nature of metal, the density of metal and acid sites determined the catalyst performance. Metal site was mainly responsible for hydrogenation of isoprene, while acid site dominantly contributed to the thioetherification and the polymerization of olefins. Moreover, a balance between metallic and acidic functions is required to arrive at a desired performance. Excessive metal sites or acid sites led to the over-hydrogenation of isoprene or the severe polymerization of olefins, respectively. 25%Mo P/Si O2 was tested for 37 h time on stream, and butanethiol conversion maintained at 100%; although isoprene conversion remarkably decreased, the selectivity to isopentenes exceeded 80% after reaction for 11 h. We suggest that the deactivation of Mo P/Si O2 is mainly ascribed to the butanethiol poisoning and the carbonaceous deposit, especially the former.

Dynamic Flow Control Strategies of Vehicle SCR Urea Dosing System

Selective Catalyst Reduction（SCR）Urea Dosing System（UDS）directly affects the system accuracy and the dynamic response performance of a vehicle.However,the UDS dynamic response is hard to keep up with the changes of the engine＇s operating conditions.That will lead to low NO_χconversion efficiency or NH_3 slip.In order to optimize the injection accuracy and the response speed of the UDS in dynamic conditions,an advanced control strategy based on an air-assisted volumetric UDS is presented.It covers the methods of flow compensation and switching working conditions.The strategy is authenticated on an UDS and tested in different dynamic conditions.The result shows that the control strategy discussed results in higher dynamic accuracy and faster dynamic response speed of UDS.The inject deviation range is improved from being between-8%and 10%to-4%and 2%and became more stable than before,and the dynamic response time was shortened from 200 ms to 150 ms.The ETC cycle result shows that after using the new strategy the NH_3 emission is reduced by 60%,and the NO_χemission remains almost unchanged.The trade-off between NO_χconversion efficiency and NH_3 slip is mitigated.The studied flow compensation and switching working conditions can improve the dynamic performance of the UDS significantly and make the UDS dynamic response keep up with the changes of the engine＇s operating conditions quickly.

Carbon nanotubes loaded with vanadium oxide for reduction NO with NH_3 at low temperature

The catalytic activity of carbon nanotubes-supported vanadium oxide(V_2O_5/CNTs) catalysts in the selective catalytic reduction(SCR) of NO with NH_3 at low temperatures(<250℃) was investigated.The effects of V_2O_5loading,reaction temperature,and presence of SO_2 on the SCR activity were evaluated.The results show that V_2O_5/CNTs catalysts exhibit high activity for NO reduction with NH_3 at low-temperatures.The catalysts also show very high stability in the presence of SO_2.More interestingly,their activities are significantly promoted instead of being poisoned by SO_2.The promoting effect of SO_2 is distinctly associated with V_2O_5 loading,particularly maximized at low V_2O_5 loading,which indicated the role of CNTs support in this effect.The promoting effect of SO_2 at low temperatures suggests that V_2O_5/CNTs catalysts are promising catalytic materials for low-temperature SCR reactions.

Comprehensive recovery of W,V,and Ti from spent selective reduction catalysts

In this study,spent WO_(3)/V_(2)O_(5)-TiO_(2) catalysts used for selective catalytic reduction were treated by a hydrometallurgical process to comprehensively recover valuable metallic elements,such as W,V,and Ti.Al and Si impurities were preferentially removed by selective micro wave-assisted alkali leaching.W and V were leached by enhanced high-pressure leaching with efficiencies estimated at 95% and 81%.The leaching of W and V followed the nuclear shrinkage model controlled by the combination of product layer diffusion and interfacial chemical reaction.A synergistic extraction was applied to separate W and V using an extractant mixture of di-(2-ethylhexyl)phosphoric acid P204 and the primary amine N1923.The extraction efficiencies of V and W reached 86.5% and 6.3%,respectively,with a separation coefficient(V/W) of 95.30.The product was precipitated after extraction to yield ammonium paratung state(APT) and NH_(4)VO_(3).The TiO_(2)catalyst carrier residue meets commercial specifications for reuse.This comprehensive recovery process with the characteristics of high-pressure leaching and synergistic extraction realizes the resourceful utilization of the spent catalysts.

Promoting effect and mechanism of neodymium on low-temperature selective catalytic reduction with NH3 over Mn/TiO2 catalysts

Series of Mn/TiO2 catalysts modified with various contents of Nd for low-temperature SCR were synthesized.It can be found that the appropriate amount of Nd can markedly reduce the take-off temperature of Mn/TiO2 catalyst to 80℃and NOx conversion is stabilized over 90%in the wide temperature range of 100-2600 C.0.1 Nd-Mn/Ti shows higher N2 selectivity and better SO2 resistance than Mn/Ti catalyst.The results reveal that Nd-doped Mn/TiO2 catalyst exhibits larger BET surface area and better dispersion of active component Mn2O3.XPS results indicate that the optimal 0.1 Nd-Mn/Ti sample possesses higher concentration of Mn4+and larger amount of adsorbed oxygen at the surface compared with the unmodified counterpart.In situ DRIFTS show that the surface acidity is evidently increased after adding Nd,especially,the Lewis acid sites,and the intermediate(-NH2)is more stable.The reaction mechanism over Mn/Ti and 0.1 Nd-Mn/Ti catalysts obey the Eley-Rideal(E-R)mechanisms under low temperature reaction conditions.H2-TPR results show that Nd-Mn/TiO2 catalyst exhibits better lowtemperature redox properties.

Role of NO in Hg^0 oxidation over a commercial selective catalytic reduction catalyst V_2O_5–WO_3/TiO_2

Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst,V2O5-WO3/TiO2,to investigate mercury oxidation in the presence of NO and O2.Mercury oxidation was improved by NO,and the efficiency was increased by simultaneously adding NO and O2.With NO and O2 pretreatment at 350°C,the catalyst exhibited higher catalytic activity for Hg^0 oxidation,whereas NO pretreatment did not exert a noticeable effect.Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O2.Although NO promoted Hg^0 oxidation at the very beginning,excessive NO counteracted this effect.The results show that NO plays different roles in Hg^0oxidation; NO in the gaseous phase may directly react with the adsorbed Hg^0,but excessive NO hinders Hg^0 adsorption.The adsorbed NO was converted into active nitrogen species（e.g.,NO2） with oxygen,which facilitated the adsorption and oxidation of Hg^0.Hg^0 was oxidized by NO mainly by the Eley-Rideal mechanism.The Hg^0 temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O2.

NH_3-SCR denitration catalyst performance over vanadium–titanium with the addition of Ce and Sb

Selective catalytic reduction technology using NH3 as a reducing agent（NH3-SCR） is an effective control method to remove nitrogen oxides. TiO2-supported vanadium oxide catalysts with different levels of Ce and Sb modification were prepared by an impregnation method and were characterized by X-ray diffractometer（XRD）, Brunauer-Emmett-Teller（BET）, Transmission electron microscopy（TEM）, Fourier transform infrared spectroscopy（FT-IR）, UV-Vis diffuse reflectance spectroscopy（UV-Vis DRS）, Raman and Hydrogen temperature-programmed reduction（H2-TPR）. The catalytic activities of V5 CexS by/TiO2 catalysts for denitration were investigated in a fixed bed flow microreactor. The results showed that cerium, vanadium and antimony oxide as the active components were well dispersed on TiO2, and the catalysts exhibited a large number of d-d electronic transitions, which were helpful to strengthen SCR reactivity. The V5 CexS by/TiO2 catalysts exhibited a good low temperature NH3-SCR catalytic activity. In the temperature range of 210 to 400℃, the V5 CexS by/TiO2 catalysts gave NO conversion rates above 90%. For the best V5Ce35Sb2/TiO2 catalyst, at a reaction temperature of 210℃, the NO conversion rate had already reached 90%. The catalysts had different catalytic activity with different Ce loadings. With the increase of Ce loading, the NO conversion rate also increased.

Hydrochlorination of acetylene using expanded multilayered vermiculite(EML-VMT)-supported catalysts

Catalyst supports have very important effects on catalyst performance.A novel expanded multilayered vermiculite（EML-VMT） is successfully used as the catalyst support for the acetylene hydrochlorination.By mixing carbon on the surface of EML-VMT[i.e.,EML-VMT-C）,the HgCl2/EML-VMT-C achieved a high acetylene conversion of 97.3%,a vinyl chloride selectivity of 100%and a turn over frequency（TOF） value of 8.83 × 10^-3s^-1 at a temperature of 140 C,an acetylene gas hourly space velocity（GHSV） of 108 h^-1,and a feed volume ratio V（HC1）/V（C2H2） of 1.15.Moreover,the HgCl2/EML-VMT-C shows good stability.The EML-VMT also shows potential in the preparation of other EML-VMT-supported catalysts.