Co-Mo系宽温耐硫变换催化剂硫化剂的选择

介绍了Co-Mo系宽温耐硫变换催化剂硫化剂的特点,并和使用CS2硫化剂硫化作了对比,效果更安全,经济,硫化效果好。

中油型加氢裂化催化剂运行评价

360万吨/年加氢裂化装置采用美国UOP公司工艺技术,并由美国UOP公司提供工艺包及配套系列催化剂,精制剂为UF-210型催化剂,裂化剂为HC-115LT型催化剂。2020年停检换剂后对催化剂性能进行评估,由产品数据可知:该催化剂选择性好、催化剂活性高、产品分布合理、装置操作弹性大、生产方案灵活,满足装置长周期运行的要求。

Single-atom catalysts based on polarization switching of ferroelectric In_(2)Se_(3) for N_(2) reduction

The polarization switching plays a crucial role in controlling the final products in the catalytic pro-cess.The effect of polarization orientation on nitrogen reduction was investigated by anchoring transition metal atoms to form active centers on ferroelectric material In_(2)Se_(3).During the polariza-tion switching process,the difference in surface electrostatic potential leads to a redistribution of electronic states.This affects the interaction strength between the adsorbed small molecules and the catalyst substrate,thereby altering the reaction barrier.In addition,the surface states must be considered to prevent the adsorption of other small molecules(such as *O,*OH,and *H).Further-more,the V@↓-In_(2)Se_(3) possesses excellent catalytic properties,high electrochemical and thermody-namic stability,which facilitates the catalytic process.Machine learning also helps us further ex-plore the underlying mechanisms.The systematic investigation provides novel insights into the design and application of two-dimensional switchable ferroelectric catalysts for various chemical processes.

Effect of NH_4^+ exchange on CuY catalyst for oxidative carbonylation of methanol

NaY and ion exchanged NaNH4Y zeolite with NH4NO3 were used as the support to prepare CuY cata‐lysts by a high temperature anhydrous interaction between the support and copper （II） acety‐lacetonate Cu（acac）2. The catalysts were used for the oxidative carbonylation of methanol to dime‐thyl carbonate （DMC） at atmospheric pressure. The textural and acidic properties of NaNH4Y zeolite and the CuY catalysts were investigated by X‐ray diffraction, scanning electron microscopy, N2 ad‐sorption‐desorption, temperature programmed reduction of H2, X‐ray photoelectron spectroscopy and temperature programmed desorption of NH3. With increasing NH4NO3 concentration, the NH4＋exchange degree increased while the crystallinity of the zeolite remained intact. Crystalline CuO was formed when the NH4＋exchange degree of NaNH4Y was low, and the corresponding CuY catalyst showed low catalytic activity. With increasing of the NH4＋exchange degree of NaNH4Y, the content of surface bound Cu＋active centers increased and the catalytic activity of the corresponding CuY catalyst also increased. The surface bound Cu＋content reached its maximum when the NH4＋ex‐change degree of NaNH4Y reached towards saturation. The CuY exhibited optimal catalytic activity with 267.3 mg/（g·h） space time yield of DMC, 6.9%conversion of methanol, 68.5%selectivity of DMC.

蒸汽转化制氢技术

为适应制氢原料价格和能源价格不断上涨的新形势,降低氢气成本,增强市场竞争能力,国外各家技术专利商在转化炉型、转化工艺、催化剂活性、能量回收、气体净化等方面作了技术改进.介绍了制氢装置在回收高、中、低温位余热,优化变换工艺及PSA工艺等方面的发展趋势.

High activity of a Pt decorated Ni/C nanocatalyst for hydrogen oxidation

The Pt decorated Ni/C nanocatalysts were prepared for hydrogen oxidation reaction（HOR） in fuel cell.By regulating the contents of Pt and Ni in the catalyst,both the composition and the structure affected the electrochemical catalytic characteristics of the Pt-Ni/C catalysts.When the Pt mass content was 3.1% percent and that of Ni was 13.9% percent,the Pt-Ni/C-3 catalyst exhibited a larger electrochemically active surface area and a higher exchange current density toward HOR than those of pure supported platinum sample.Our study demonstrates a feasible approach for designing the more efficient catalysts with lower content of noble metal for HOR in fuel cell.

Optimum Operating and Regeneration Parameters of ZnI2 Catalyst for Converting Methanol to Triptane:An Ideal Component of Unleaded Aviation Gasoline

Conversion of methanol(MeOH) to 2,2,3-trimethylbutane(triptane) over zinc iodide(ZnI_2)catalyst was investigated in a closed batch reactor.Optimum operating parameters were searched and catalyst deactivation and regeneration behaviors were discussed.The fresh,spent and regenerated catalysts were characterized by XRD,TG and XRF measurements to elucidate the related mechanism.The experimental results showed that the triptane yield reached up to 12.2% under the process conditions,including a reaction temperature of 200℃,an initial pressure of 0.35 MPa,a reaction time of 2 h,and a Me OH to ZnI_2 molar ratio of 2.The catalyst was gradually deactivated after several run cycles.A small amount of iodine was lost and a certain amount of ZnO was formed on the deactivated ZnI_2 catalyst.Deactivation of the catalyst could be attributed to the reduction of ZnI_2 amount,resulted from iodine loss and formation of Zn O.It was firstly pointed out from our work that the deactivated catalyst could be well regenerated by the hydrogen iodide(HI) and the tert-butanol compensation method,wherein the latter was added as an initiator into the reaction system.The activity recovery of the deactivated(spent) catalyst might be related to the reformation of ZnI_2 and acceleration of the initiation step of this reaction.

Simulation for Transesterification of Methyl Acetate and n-Butanol in a Reactive and Extractive Distillation Column Using Ionic Liquids as Entrainer and Catalyst

A new reactive and extractive distillation process with ionic liquids as entrainer and catalyst （RED-IL）was proposed to produce methanol and n-butyl acetate by transesterification reaction of methyl acetate with n-butanol. The RED-IL process was simulated via a rigorous model, and high purity products of methanol and n-butyl acetate can be obtained in such a process. The effects of reflux ratio, feed mode, holdup, feed location, entrainer ratio and catalyst concentration on RED-IL process were investigated. The conversion of methyl acetate and purities of products increase with the holdup in column, entrainer ratio and catalyst content. An optimal reflux ratio exists in RED-IL process. Comparing to the mixed-feed mode, the segregated-feed mode is more effective, in which the optimal feed locations of reactants exist.

Studies on Catalyst Deactivation Rate and Byproducts Yield during Conversion of Methanol to Olefins

The conversion of methanol to olefins (MTO) over the SAPO-34 catalyst in fixed-bed microreactor was studied. The effect of reaction temperatures for methanol conversion to olefins and byproducts was investigated. A temperature of 425 ℃ appeared to be the optimum one suitable for conversion of methanol to olefins. Since the presence of water could increase the olefins selectivity, the methanol conversion reactions with mixed water/methanol feed were also studied. The effect of weight hourly space velocity on conversion of methanol was also studied. The results indicated that the olefins selectivity was significantly increased as WHSV increased till approximately 7.69 h-1 then it began to level off. Different factors affecting the catalyst deactivation rate was studied, showing that the catalyst deactivation time was dependent on reaction conditions, and temperatures higher and lower than the optimal one made the catalyst deactivation faster. Adding water to methanol could slow down the catalyst deactivation rate.

Kinetic Study of Esterification of Lactic Acid with Isobutanol and n-Butanol Catalyzed by Ion-exchange Resins

The esterification reactions of lactic acid with isobutanol and n-butanol have been studied in the presence of acid ion-exchange resin Weblyst D009. The influences of catalyst loading, stirrer speed, catalyst particle size, initial reactant molar ratio and temperature on the reaction rate have been examined. Experimental kinetic data were correlated by using the pseudo-homogeneous, Langnluir-Hinshelwood and Eley-Rideal models. Nonideality of the liquid phase was taken into account by using activities instead of molar fractions. The activity coefficients were calculated according to the group contribution method UNIFAC. Provided that the nonideality of the liquid is taken into account, the esterification kinetics of lactic acid with isobutanol and n-butanol catalyzed by the acid ion-exchange resin can be described using all threemodels with reasonable errors.

Preparation,characterization and photocatalytic activity of sulfuric acid-modified titanium-bearing blast furnace slag

The feasibility of reducing Cr(VI)from the aqueous solution by sulfuric acid-modified titanium-bearing blast furnace slag(SATBBFS)as a photocatalyst was investigated.The photocatalysts were examined by X-ray diffraction(XRD),UV-vis diffuse reflectance spectra,thermogravimetric analysis(TG)and Fourier transform infrared spectroscopy(FTIR).The photocatalytic activities of the different catalysts were evaluated by the photocatalytic reduction of Cr(VI)under UV-vis light irradiation.The results show that the photocatalytic activities of SATBBFS catalysts are strongly dependent on CaTiO3-to-TiO2 mass ratio,adsorption capacity and surface acidity,and SATBBFS calcined at 400°C shows a higher photocatalytic activity compared with other catalysts.

Reaction kinetics for synthesis of sec-butyl alcohol catalyzed by acid-functionalized ionic liquid

The acid-functionalized ionic liquid([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance(NMR) and Fourier transform infrared spectroscopy(FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a homogeneous kinetic model was established. The results show that the reaction heat ΔH is 10.94 × 103J·mol-1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea-are 60.38 × 103 and 49.44 × 103J·mol-1,respectively.

Catalytic conversion of ethyl lactate to 1,2-propanediol over CuO

An efficient conversion of biomass-derived ethyl lactate to 1,2-propanediol(1,2-PDO) over CuO was investigated.Among the catalysts we tested, CuO, Cu2 O and Co showed excellent catalytic activity for the conversion of ethyl lactate to 1,2-PDO in water, and CuO was more active and gave the best result. The 1,2-PDO yield of 93.6% was achieved when Zn acted as a reductant. The results indicated that in situ formed hydrogen by the oxidation of Zn in water is more effective than gaseous hydrogen, which failed to produce the 1,2-PDO from ethyl lactate.From a practical point of view, the present method may provide a useful route for the production of 1,2-PDO from ethyl lactate.

Effects of Activation Atmospheres on Structure and Activity of Mo-based Catalyst for Synthesis of Higher Alcohols

Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H2, syngas （H2/CO=2/1）, and pure CO. The cat- alysts structures were characterized by X-ray diffraction , X-ray absorption fine structure, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The catalytic per- formance for the higher alcohol synthesis from syngas was tested. The pure H2 treatment showed a high reduction capacity. The presence of a large amount of metallic CoO and low valence state Mo^φ＋ （0〈φ〈2） on the surface suggested a super activity for the CO dissoci- ation and hydrogenation, which promoted hydrocarbons formation and reduced the alcohol selectivity. In contrast, the pure CO-reduced catalyst had a low reduction degree. The Mo and Co species at the catalyst mainly existed in the form of Mo^4＋ and Co^2＋. The syngas- reduced catalyst showed the highest activity and selectivity for the higher alcohols synthesis. We suggest that the syngas treatment had an appropriate reduction capacity that is between those of pure H2 and pure CO and led to the coexistence of multivalent Co species as well as the enrichment of Mo~＋ on the catalyst＇s surface. The synergistic effects between these active species provided a better cooperativity and equilibrium between the CO dissociation, hydrogenation and CO insertion and thus contributed beneficially to the formation of higher alcohols.

Synthesis, Characterization and Evaluation of Sulfur Transfer Catalysts for FCC Flue Gas

In this work, Zr-M(M=Cu, Mn, Ce) type sulfur transfer agent was prepared by impregnation method. Under the condition similar to that in the regenerator of FCC units, the influence of different active metal components and their contents on sulfur transfer agent were investigated. Moreover, the crystalline structure of sulfur transfer agent was characterized by X-ray diffraction(XRD) and Fourier transforms infrared spectroscopy(FT-IR). The result showed that the Zr-Mn sulfur transfer agent could effectively reduce the SO2 content in FCC regenerator flue gas, featuring high SO2 adsorption capacity. The sulfur transfer agent was inactivated in 40—60 min during the test. In the course of reduction reaction, after several reaction cycles, the formation of SO2 ceased and only H2 S was detected as the reduction product.

Recent developments of nanocarbon based supports for PEMFCs electrocatalysts

Nanocarbons,widely and commonly used as supports for supported Pt-based electrocatalysts in PEMFCs,play a significant role in Pt dispersion and accessibility,further determining their corresponding electrocatalytic performance.This paper provides an overview of the nanoarchitectures and surface physicochemical properties of nanocarbons affecting the electrocatalyst performance,with an emphasis on both physical characteristics,including pore structure,and chemical properties,including heteroatom doping and functional carbon-based supports.This review discusses the recent progress in nanocarbon supports,guides the future development direction of PEMFC supports,and provides our own viewpoints for the future research and design of PEMFCs catalysts,advancing the commercialization of PEMFCs.

Rare Earth Metals Ion-exchanged β-Zeolites as Supports of Platinum Catalysts for Hydroisomerization of n-Heptane

A series of Pt catalysts supported on the Hβ-zeolite that is ion-exchanged with the rare earth metal ions of Ce（III） and La（III）,are prepared by impregnation,characterized by inductively coupled plasma （ICP）,X-ray diffraction （XRD）,BET,temperature-programmed desorption of ammonia （NH3-TPD）,temperature-programmed reduction of hydrogen （H2-TPR） and H2-chemisorption techniques,and evaluated in the hydroisomerization of n-heptane with an atmospheric fixed-bed reactor.The reaction temperature,time on stream,space velocity,and the ratio of H2/n-heptane are changed to get the optimal conditions.The Ce（III） and La（III）-exchanged Hβ-zeolites exhibit higher selectivity for isomerized products than the neat Hβ-zeolite.Moreover,the Ce（III）-exchanged catalysts give higher conversions of n-heptane,whereas the La（III）-exchanged ones do not show any improvement in con-version.Under optimal conditions,the catalyst with 0.4% （by mass） Pt and 0.5% （by mass） Ce loading presents very high selectivity of isomerized products of 95.1% coupled with high n-heptane conversion of 68.7%.Effects of the ion-exchange of Ce（III） and La（III） on the catalytic performance are discussed in relation with the physico-chemical properties of catalysts.

A Novel γ-Alumina Supported Fe-Mo Bimetallic Catalyst for Reverse Water Gas Shift Reaction

In reverse water gas shift （RWGS） reaction COa is converted to CO which in turn can be used to pro- duce beneficial chemicals such as methanol. In the present study, Mo/AlaO3, Fe/AlaO3 and Fe-Mo/Al2O3 catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction （XRD）, Brunauer-Emmett-Teller （BET） method, inductively coupled plasma atomic emission spectrometer （ICP-AES）, temperature programmed reduction （H2-TPR）, CO chemisorption, energy dispersive X-ray （EDX） and scanning electron microscopy （SEM） techniques. Kinetic properties of all catalysts were investigated in a batch re- actor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/AlzO3 catalyst enhances its activity as compared to Fe/AlaO3. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/AlzO3 catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fez（MoO4）3 phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fez（MoO4）3 phase has low reducibility, therefore the Fe2（MoO4）3 phase significantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al2O3 catalyst. Overall, this study introduces Fe-Mo/Al2O3 as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.