Hydrogenation of Olefins Catalyzed by Highly Active Titanocene/NaH or n-BuLi Catalyst Systems

The effects of the substituents on the cyclopentadienyl ring and the reducing agents on the catalytic activity and the stability of titanocene/NaH or n BuLi systems for the hydrogenation of olefins were investigated. For the catalyst systems composed of titanocene/NaH or n BuLi, the nature and the number of the substituents on the cyclopentadienyl ring control the catalytic behavior of those two systems. The effect of the reducing agent on the catalytic activity is relatively small. In addition, the characters of the hydrogenation of various olefins catalyzed respectively by Cp 2TiCl 2/NaH or n BuLi systems were compared.

Effects of porous oxide layer on performance of Pd-based monolithic catalysts for 2-ethylanthraquinone hydrogenation

Pd/oxide/cordierite monolithic catalysts(oxide = Al_2O_3, SiO_2 and SiO_2\\Al_2O_3) were prepared by the impregnation method. The results of ICP, XRD, SEM–EDX, XPS and N_2 adsorption–desorption measurements revealed that the Pd penetration depth increased with increasing the thickness of oxide layer, and the catalysts with Al_2O_3 layers had the larger pore size than those with SiO_2 and SiO_2\\Al_2O_3 layers. Catalytic hydrogenation of 2-ethylanthraquinone(eA Q), a key step of the H_2O_2 production by the anthraquinone process, over the various monolithic catalysts(60 °C, atmosphere pressure) showed that the monolithic catalyst with the moderate thickness of Al_2O_3 layer(about 6 μm) exhibited the highest conversion of e AQ(99.1%) and hydrogenation efficiency(10.0 g·L^(-1)). This could be ascribed to the suitable Pd penetration depth and the larger pore size, which provides a balance between the distribution of Pd and accessibility of active sites by the reactants.

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.

Preparation of Ni/bentonite catalyst and its applications in the catalytic hydrogenation of nitrobenzene to aniline

Ni supported on bentonite was prepared by the impregnation method with different nickel contents, applied to the hydrogenation of nitrobenzene to aniline in a fixed-bed reactor, and it was characterized by X-ray diffraction（XRD）, H2-temperature programmed reduction（H2-TPR）, and X-ray photoelectron spectrometry（XPS）. The results showed that Ni/bentonite catalyst with 20 wt% nickel content provided a higher conversion of nitrobenzene and selectivity of aniline compared to other catalysts. NiO was the precursor of the active component of the catalyst, and the small crystallite size as well as the highly dispersed NiO on the Ni/bentonite-20 catalyst, contributed to the catalytic performance. The hydrogenation of nitrobenzene was carried out at 300℃ with a H_2 gaseous hourly space velocity of 4800 ml·（g cat）^-1·h^-1and a nitrobenzene liquid hourly space velocity of4.8 ml·（g cat）^-1·h^-1 over Ni/bentonite-20. A 95.7% nitrobenzene conversion and 98.8% aniline selectivity were obtained. While the nitrobenzene liquid hourly space velocity was 4.8 ml·（g cat）^-1·h^-1, the yield of aniline was more than 95.0% during a 10-hour reaction.

Effect of preparation methods on the structure and catalytic performance of Fe–Zn/K catalysts for CO2 hydrogenation to light olefins

Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5^+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.

Promotional Effect of CoO(OH) on Selective Hydrogenation of Maleic Anhydride to γ-Butyrolactone over Supported Ruthenium Catalyst

A decorated ruthenium catalyst was prepared by the coprecipitation method and used for the selective hydrogenation of maleic anhydride(MA) to γ-butyrolactone(GBL). The as-prepared catalyst was characterized by XRD, TGDTG and N2 adsorption techniques. The characterization tests revealed that the catalyst carrier was composed of monoclinic zirconia(m-ZrO2) and hydroxyl cobalt oxide(CoO(OH)). The hydrogenation results showed that the content of CoO(OH), the reaction temperature, the hydrogen pressure and the reaction time significantly affected the catalytic selectivity to GBL. The promotional effect of CoO(OH) was remarkable, which led to an obvious increase in GBL selectivity. An 100% MA conversion and 92.0% selectivity to GBL were achieved over the Ru/ZrO2-CoO(OH)(35%) catalyst in water solvent under the conditions involving a reaction temperature of 180 ℃, a hydrogen pressure of 3.0 MPa, and a reaction time of 6 h.

Successful Application of Novel α-Methylstyrene Hydrogenation Catalyst at Yanshan Petrochemical Company

The SHP-A1 type catalyst for hydrogenation of α-methylstyrene(AMS)developed by the SINOPEC Shanghai Petrochemical Research Institute(SPRI)has been successfully applied in the No.1 phenol unit at the Third Chemical Plant of Yanshan Petrochemical Company at the first attempt of commissioning.The said catalyst is the first AMS hydrogenation catalyst developed

A New Catalyst for Hydrogen Transfer Hydrogenation of Acetophenone

A new C-2-symmetric diamine/diphosphine Ruthenium (II) complex, RuCl2P2N2H4, was used as an excellent catalyst to carry out the catalytic hydrogen transfer reduction of acetophenone. The conversion of acetophenone to 2-phenylethanol was up to 99% under the following reaction conditions: substrate:Ru:(CH3)(2)CHOK = 200:1:12; reaction temperature of 65 degrees C; reaction time of 2 h; normal pressure. A hydride transfer mechanism was also discussed.

CATALYTIC PERFORMANCE OF MIXED-BIMETALLIC RUTHENIUM CARBONYL CLUSTERDERIVED CATALYSTS IN CO HYDROGENATION

The bimetallic catalysts prepared from SiO_2-supported Ru-Co,Ru- Fe and Ru-Mo carbonyl clusters exhibited high yields and selectivities towards oxygenates such as C_1-C_5 from CO+H_2,in contrast to the catalysts prepared from homometallic and bimetallic Ru,Ru-Ni,Ru-Rh,Ru-Mn,and Ru- Cr carbonyl clusters.The FTIR investigation revealed that the 1584 cm^(-1) species plays an important role in the formation of oxygenates in CO hydrogenation,which is possibly assigned to surface formyl species.

CARBONACEOUS PRODUCTS OF POLYMER-PALLADIUM COMPLEXES AS CATALYSTS FOR THE HYDROGENATION OF METHYL ACRYLATE

Many catalysts were pcrpared by carbonization of ion exchange resin-PdCl_2 complexes at high temperature in nitrogen, hydrogen atmosphere. The rates for the hydrogenation of methyl acrylate and the amounts of Pd elution of the carbonaceous products were measured and compared with those of commercial Pd/C catalyst. It indicates that the carbonaceous products are less active than Pd/C. However, the leaching of Pd from carbonaceous products is very small and much less than that from Pd/C.

STUDIES ON THE STATE OF PALLADIUM AND HYDROGENATION ACTIVITY OF RESIN SUPPORTED PALLADIUM──TIN OXIDE CATALYSTS

Several Pd--SnO2/ D3520 and Pd--PbO / D3520 catalysts with Pd/ D3J20, SnO2 / D3520 and PbO / D3520 catalysts as rference were studied by means of IR and XPS. Interaction between Pd and the second metal or between metal and support was observed. Results show that there is a strong interaction between Pd and the second metal, but there is not an obvious interaction between metal and support. The active constituent is Pd￣0. Hydrogenation activity of the catalysts is altered because of the interaction between Pd and the second,metal.The activity of the catalysts for hydrogenation has relation to outer layer valence electron density of Pd.

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.

In situ assembly of metal-organic framework-derived N-doped carbon/Co/CoP catalysts on carbon paper for water splitting in alkaline electrolytes

High-performance and cost-effective catalysts for water splitting are key components of hydrogen-based energy technologies. Metal-organic framework(MOF)-derived metal phosphide composites have immense potential as highly active and stable electrocatalysts but suffer from the poor efficacy of available electrode assembly methods. In this study, an MOF-derived nitrogen-doped porous carbon/Co/Co P/carbon paper(NC/Co/Co P/CP) composite electrode was assembled by electrophoretic deposition and post-processing reactions. The binder-free electrode showed good catalytic activity, significantly higher than that of traditional electrodes. The electrode required overpotentials of 208 and 350 m V to achieve a current density of 10 m A/cm^2 for the hydrogen and oxygen evolution reactions, respectively. This facile synthetic method provides a promising route for designing metal-doped and multi-metal phase MOF-derived composite electrodes for energy storage and conversion devices.

Simultaneous recovery of carbon and sulfur resources from reduction of CO_2 with H_2S using catalysts

An approach to the simultaneous reclamation of carbon and sulfur resources from CO2 and H2S has been proposed and effectively implemented with the aid of catalysts. A brief thermodynamic study reveals the potential of direct reduction of CO2 with H2S（15：15 mol% balanced with N2） for selective production of CO and elemental sulfur. The experiments carried out in a fixed-bed flow reactor over the temperature range of 400–800 °C give evidence of the importance of the employment of catalysts. Both the conversions of the reactants and the selectivities of the target products can be substantially promoted over most catalysts studied. Nevertheless, little difference appears among their catalytic performance. The results also prove that the presence of CO2 can remarkably enhance H2S conversion and the sulfur yield in comparison with H2S direct decomposition. A longtime reaction test on Mg O catalyst manifests its superior durability at high temperature（700 °C） and huge gas hourly space velocity（100,000 h-1）. Free radicals initiated by catalysts are supposed to dominate the reactions between CO2 and H2S.

Influence of Zr, Ce, and La on Co_3O_4 catalyst for CO_2 methanation at low temperature

The Co3O4 and Zr-,Ce-,and La-Co3O4 catalysts were prepared,characterized,and applied to produce CH4 from CO2 catalytic hydrogenation in low temperature as 140–220℃.The results indicated that the addition of Zr,Ce,or La to the Co3O4 decreased the crystallite sizes of Co and the outer-shell electron density of Co^3＋,and increased the specific surface area,which would provide more active sites for the CO2 methanation.Especially,the addition of Zr also changed the reducing state of Co3O4 via an obvious change in the interaction between Co3O4 and ZrO2.Furthermore,Zr doped into the Co3O4 increased the basic intensity of the weak and medium basic sites,as well as the amount of Lewis acid sites,and Bronsted acid sites were also found on the Zr-Co3O4 surface.The introduction of Zr,Ce,or La favored the production of CH4,and the Zr-Co3O4catalyst exhibited the highest CO2 conversion（58.2%）and CH4 selectivity（100%）at 200℃,and 0.5 MPa with a gaseous hourly space velocity of 18,000 ml·g^-1（cat）·h^-1,and the catalytic activity of CO2methanation for the Zr-,Ce-,and La-Co3O4 exhibited more stable than Co3O4 in a 20-h reaction.

RAMAN SPECTRA OF HYDROGEN ADSPECIES ON AMMONIA SYNTHESIS IRON CATALYST

Raman peaks at 1951 and 2165 cm^(-1) can be confirmed further by H_2/D_2 isotope exchange as H-adspecies on the doubly promoted iron catalyst for ammonia synthesis and are probably ascribed to two terminally adsorbed H-species.

Enrichment of Ni-Mo-V via pyrometallurgical reduction from spent hydrogenation catalysts and the multi-reaction mechanism

Spent hydrogenation catalysts are important secondary resources due to richness in the valuable metals of Ni,Mo and V.Recovery of valuable metals from spent catalysts has high economic value and environmental benefits since they are hazardous wastes as well.Traditional recycling processes including hydrometallurgical leaching and soda roasting-leaching have disadvantages such as generating large amounts of wastewater,long process,and low recovery efficiency of valuable metals.Thus,this paper proposed synergistic enrichment of Ni,Mo and V via pyrometallurgical reduction at 1400-1500℃.The melting temperature and viscosity of slag were reduced through slag designing by software FactSage 7.1.The phase diagram of Al_(2)O_(3)-Cap-SiO_(2)-Na_(2)O-B_(2)O_(3)was drawn,and low-temperature region(≤1300℃)was selected as target slag composition.Ni,Mo,and V can be collaborative captured and recovered through the mutual solubility at molten state.Increasing the melting temperature and the amount of CaO,Na_(2)O and C were conducive to improving the metals recovery rates.The kilogram-scale experiments were carried out,and the recovery efficiencies of Ni,Mo and V were 98.3%,95.3%and 97.9%under optimized conditions:at 1500℃,with the basicity of 1.0,13.1 wt%SiO_(2),7.0 wt%B_(2)O_(3),7.7 wt%Na_(2)O and 20.0wt%C.The distribution behavior of valuable metals was clarified by investigating the melting process of slag and the reduction in valuable metals.Ni was preferentially reduced and acted as a capturing agent,which captured other metals to form NiMoV alloys.

Advances in the production technology of hydrogen peroxide

This article mainly summarizes various aspects of hydrogen peroxide(H2O2)production through the anthraquinone route,including hydrogenation catalysts,working solution,regeneration technique,hydrogenation reactors,and environmental protection.The advances and breakthrough of SINOPEC in the production of H2O2 through the anthraquinone route is presented in this review,highlighting recent innovative technology on these aspects developed independently.The technical prospect and scientific challenges associated with the direct synthesis method from hydrogen and oxygen are also briefly discussed.

Self-assembled multifunctional Fe_(3)O_(4) hierarchical microspheres: high-efficiency lithium-ion battery materials and hydrogenation catalysts

Self-assembled Fe_(3)O_(4)hierarchical microspheres(HMSs) were prepared by a one-pot synchronous reduction–self-assembling (SRSA) hydrothermal method.In this simple and inexpensive synthetic process,only glycerol,water,and a single iron source (potassium ferricyanide (K3[Fe(CN)6]))were employed as reactants without additional reductants,surfactants,or additives.The iron source,K3[Fe(CN)6],and glycerol significantly affected the synthesis of Fe_(3)O_(4)HMSs.Fe_(3)O_(4)HMSs with a self-assembled spherical shape readily functioned as high-performance anode materials for lithiumion batteries with a specific capacity of>1000 mA h g^(-1)at0.5 A g^(-1)after 270 cycles.Further charging and discharging results revealed that Fe_(3)O_(4)HMSs displayed good reversible performance (>1000 mA h g^(-1)) and cycling stability (700 cycles) at 0.5 A g^(-1).Furthermore,as multifunctional materials,the as-obtained Fe_(3)O_(4)HMSs also exhibited high saturation magnetization (99.5 emu g^(-1)) at room temperature (25°C) and could be further employed as efficient and magnetically recyclable catalysts for the hydrogenation of nitro compounds.

Hierarchical molybdenum disulfide nanosheet arrays stemmed from nickel-cobalt layered double hydroxide/carbon cloth for highly-efficient hydrogen evolution reaction

The hierarchical structure of molybdenum disulfide(MoS2)nanosheet arrays stemmed from nickelcobalt layered double hydroxide(NiCo-LDH)/carbon cloth was prepared by growing the MoS_(2) nanosheet arrays onto the NiCo-LDH template which was pre-deposited onto the carbon cloth substrate.In this electrode configuration,carbon cloth is the three dimensional and conductive skeleton;NiCo-LDH nanosheets,as the template,ensure the oriented growth of MoS2 nanosheet arrays.Therefore,more MoS_(2) active sites are exposed and the catalyst exhibits good hydrogen evolution reaction activity.