Regeneration of Nickel-Molybdenum Catalysts DN-3531 and Criterion 514 Used in Kerosene and Gas Oil Hydrotreating by Supercritical Carbon Dioxide Extraction

Results of research of supercritical fluid CO2-regeneration process of Nickel-Molybdenum Catalysts DN-3531 and Criterion 514 are given. Regeneration was carried out with the use of pure supercritical carbon dioxide and mixture of supercritical carbon dioxide and various polar cosolvents. Regeneration process is carried out along isotherms, in the temperature range of 323 - 383 K, at pressures of P = 20 MPa and 30 MPa. Results of surface assessment of the catalyst samples regenerated show high effectiveness of suggested method.

Recovery of vanadium and molybdenum from spent petrochemical catalyst by microwave-assisted leaching

The study of the leaching of vanadium(V) and molybdenum(Mo) from spent petrochemical catalysts in sodium hydroxide(NaO H) medium was performed using two approaches, namely, conventional leaching and microwave-assisted leaching methods. The influence of microwave power, leaching time, leaching temperature, and NaOH concentration on the leaching efficiency of spent petrochemical catalyst was investigated. Under microwave-assisted conditions(600 W, 10 min, 90°C, 2.0 mol·L^(-1) NaOH, and 0.20 g·mL^(-1) solid–liquid ratio), the leaching efficiencies of V and Mo reached 94.35% and 96.23%, respectively. It has been confirmed that microwave energy has considerable potential to enhance the efficiency of the leaching process and reduce the leaching time. It is suggested that the enhancement of the leaching efficiencies of V and Mo can be attributed to the existence of a thermal gradient between solid and liquid and the generation of cracks on the mineral surface.

Chemical Treatment to Recover Molybdenum and Vanadium from Spent Heavy Gasoil Hydrodesulfurization Catalyst

Large quantities of spent hydrodesulfurization (HDS) catalysts are available from petrochemical industry. Disposal of spent catalyst is a problem as it falls under the category of hazardous industrial waste due to its vanadium concentration. Most of these catalysts are usually supported on alumina containing a variable percentage of elements such as nickel or molybdenum. Hence these catalysts contain environmentally critical, and economically valuable metals such as molyb denum, vanadium, and, nickel. In this paper, a spent HDS catalyst was treated with caustic soda solution. Parameters such as temperature, time, and NaOH solution concentration have been studied thoroughly, in order to settle the appropriate conditions for the maximum recovery of molybdenum and vanadium. Under the best leaching conditions (20 %w NaOH, room temperature, 2 h) about 95% recovery of Mo and V was achieved, and the recovery of nickel obtained was of 99% in the form of NiAlO4.

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.

Amine-functionalized boehmite nanoparticle-supported molybdenum and vanadium complexes:Efficient catalysts for epoxidation of alkenes

Boehmite nanoparticles with a high surface area and a high degree of surface hydroxyl groups were covalently functionalized by 3‐（trimethoxysilyl）‐propylamine to support vanadium‐oxo‐sulfate and molybdenum hexacarbonyl complexes. These supported catalysts were then characterized by Fou‐rier‐transform infrared spectroscopy, powder X‐ray diffraction, thermogravimetry and differential thermal analysis, X‐ray‐photoelectron spectroscopy, elemental analysis, inductively coupled plasma, and transmission electron microscopy techniques. The catalysts were subsequently used for the epoxidation of cis‐cyclooctene, and the experimental procedures were optimized. The progress of the reactions was investigated by gas‐liquid chromatography. Recycling experiments revealed that these nanocatalysts could be repeatedly used several times for a nearly complete epoxidation of cis‐cyclooctene. The optimized experimental conditions were also used successfully for the epoxida‐tion of some other substituted alkenes.

Effect of Reduction Temperature on Hydrofining Performance of Supported Molybdenum Phosphide Catalyst

A series of supported molybdenum phosphide catalysts were prepared by impregnation method. XRD, TG-DTG, XPS and BET were used to study the phase, compositions and surface areas of the prepared catalysts. A model reactant containing thiophene, pyridine and cyclohexene was used for the measurements of catalytic activities. The effect of reduction temperature on catalytic activities was investigated. The analysis results by XRD and BET are very different when the reduction temperature is changed from 400 to 900 ℃. MoP/γ-Al2O3 catalysts and CoMoP/γ-Al2O3 catalysts prepared at the reduction temperature of 500 ℃ are the most active ones.

Preparation of high vinyl polybutadiene/sepiolite nanocomposite by in-situ polymerization with new molybdenum-based catalyst

The dispersion of functional nanometer materials in polyolefin/clay nanocomposites is a key factor to determine the performances of mate-rials[1].In this research,the sepiolite with high specific surface area and good adsorption was introduced into the molybdenum-based butadiene polymerization system.Sepiolite-supporting MoCl5(Mo)function as the main catalysts,together with the alkyl aluminum(Al)substituted by m-cresol to form the butadiene coordination polymerization catalyst system to prepare high vinyl polybutadiene(HVPB)/sepiolite(Sep)nanocomposite.

INFLUENCE OF MOLYBDENUM ADDITIVE ONTO THE Co/CuLaZr CATALYSTS

The alcohol synthesis with a good proportion of higher alcohols was studied over promoted Co/CuLaZr catalysts. the molybdenum addition improved greatly the performance. The results of probe molecule tests could be used to explain the effects.

THE STUDY OF MOLYBDENUM PHOSPHIDE AS CATALYST FOR SIMULTANEOUS HDN, HDS AND HDY

Transition metal molybdenum phosphides were prepared by direct reduction of an amorphous phosphate precursor in hydrogen at relatively low temperature (650 ℃). XRD (X ray diffraction analysis) measurements showed that pure molybdenum phosphide formed after the reduction with H 2. The reactivity was determined in a continuous flow microreactor at a H 2 pressure of 3.0 MPa. A sample of prepared molybdenum phosphide catalyst diluted with γ Al 2O 3 (20% phosphate precursor) was used for simultaneous HDN (Hydrodenitrogenation), HDS (Hydrodesulfurization) and HDY(Hydrogenation of aromatics). The influences of space velocity, flow rate of hydrogen, reaction time and temperature on hydrotreating performance were studied. Pyridine, thiophene and cyclohexene were used as model compounds, their contents were respectively 5%, 5% and 20%. Cyclohexane was used as the solvent.

废加氢催化剂熔炼合金酸浸液中钼、镍萃取分离研究

针对废加氢催化剂熔炼合金加压氧化酸浸液,采用N235萃取剂萃取分离回收其中的钼与镍。考察了酸浸液中SO_(4)^(2‒)浓度、酸浸液pH值、有机相组成、有机相与水相的相比V(O)/V(A)对钼萃取过程的影响,以及氨水浓度、相比对钼反萃过程的影响。结果表明,较优萃取条件为酸浸液中SO_(4)^(2‒)浓度为1.2 mol/L、酸浸液pH值为0.9、有机相组成(V/V)为10%N235/15%仲辛醇/75%磺化煤油及V(O)/V(A)为1/1,单级钼的萃取率可达99.80%,而镍的萃取率仅为2.35%;较优反萃条件为反萃剂6 mol/L氨水与V(O)/V(A)为1/1,单级钼的反萃率可达90.63%。含镍萃余液及含钼反萃液通过后续的常规净化、结晶制备得到的三氧化钼与硝酸镍,从而实现了废加氢催化剂中有价金属的循环利用。

原子尺度钼系加氢脱硫催化剂的研究进展与展望

深入探讨了原子尺度钼系加氢脱硫催化剂在加氢脱硫反应中的研究进展。重点关注了MoS_(2)和Co(Ni)MoS微观结构对催化性能的影响,以及活性氢原子生成、硫化条件对催化剂结构和活性的影响。探讨了不同类型MoS_(2)和Co(Ni)MoS边缘结构与加氢脱硫性能的构效关系,强调了MoS_(2)边缘的硫-氢基团在反应中的关键作用。此外,详细讨论了噻吩分子在催化剂表面的吸附方式,加深了对噻吩的加氢脱硫机理的了解。最后,强调了载体Al_(2)O_(3)表面氢溢流效应的重要性,通过调控氧化铝载体表面的羟基基团与钼酸根的相互作用,提高了催化活性。总体而言,这些研究结果突显了微观结构在催化活性调控中的关键作用,为提高工业加氢脱硫反应速率提供了有力的支持。

氮掺杂二硫化钼纳米催化剂的电催化析氢性能

以钼酸钠为钼源,L-半胱氨酸为硫源和还原剂,双氰胺为氮源,采用水热法合成了一系列氮掺杂二硫化钼纳米催化剂(N-MoS_(2))。通过XRD、SEM、XPS、Raman等手段表征了不同N掺杂量的N-MoS_(2)催化剂的形貌、元素分布、晶体结构和电子性质。表征结果表明,合成的N-MoS_(2)催化剂均为纳米片层组成的花球,N原子均匀掺杂进了MoS_(2)晶格中。N掺杂使得N原子周围的Mo和S原子的电子密度增加,生成更多具有催化活性的不饱和配位点。采用电化学工作站在酸性介质中测试了催化剂的线性扫描伏安曲线和塔菲尔斜率,评价了N-MoS_(2)纳米催化剂的电催化析氢(HER)性能。结果表明,MoS_(2)催化剂和N-MoS_(2)催化剂上的析氢反应均通过Volmer-Heyrovsky路径进行。MoS_(2)催化剂上析氢反应速控步骤为Volmer反应,N-MoS_(2)催化剂上析氢反应的速控步骤为Heyrovsky反应。与MoS_(2)催化剂相比,N-MoS_(2)催化剂的塔菲尔斜率较低,析氢反应速率较快,显示出更好的电催化析氢性能。尤其当N与Mo的原子为0.1时(N/Mo=0.1),制备的N-MoS_(2)-0.1催化剂表现出最好的电催化析氢性能,其塔菲尔斜率为60mV/dec。N-MoS_(2)催化剂的电催化活性提高可归结为不饱和配位点暴露量的增加和富电子的Mo对Mo-H*的弱化。

Active MoS_(2)-based electrode for green ammonia synthesis

Nitrogen electro-reduction under mild conditions is one promising alternative approach of the energyconsuming Haber-Bosch process for the artificial ammonia synthesis.One critical aspect to unlocking this technology is to discover the catalysts with high selectivity and efficiency.In this work,the N_(2)-to-NH_(3)conversion on the functional MoS_(2)is fully investigated by density functional theory calculations since the layered MoS_(2)provides the ideal platform for the elaborating copies of the nitrogenase found in nature,wherein the functionalization is achieved via basal-adsorption,basal-substitution or edge-substitution of transition metal elements.Our results reveal that the edge-functionalization is a feasible strategy for the activity promotion;however,the basal-adsorption and basal-substitution separately suffer from the electrochemical instability and the NRR inefficiency.Specifically,MoS_(2)functionalized via edge W-substitution exhibits an exceptional activity.The energetically favored reaction pathway is through the distal pathway and a limiting potential is less than 0.20 V.Overall,this work escalates the rational design of the high-effective catalysts for nitrogen fixation and provides the explanation why the predicated catalyst have a good performance,paving the guidance for the experiments.

High-throughput calculation-based rational design of Fe-doped MoS_(2) nanosheets for electrocatalytic p H-universal overall water splitting

Electrocatalytic water splitting is crucial for H2generation via hydrogen evolution reaction(HER)but subject to the sluggish dynamics of oxygen evolution reaction(OER).In this work,single Fe atomdoped MoS_(2)nanosheets(SFe-DMNs)were prepared based on the high-throughput density functional theory(DFT)calculation screening.Due to the synergistic effect between Fe atom and MoS_(2)and optimized intermediate binding energy,the SFe-DMNs could deliver outstanding activity for both HER and OER.When assembled into a two-electrode electrolytic cell,the SFe-DMNs could achieve the current density of 50 mA cm^(-2)at a low cell voltage of 1.55 V under neutral condition.These results not only confirmed the effectiveness of high-throughput screening,but also revealed the excellent activity and thus the potential applications in fuel cells of SFe-DMNs.

固定床甲醇氧化制甲醛铁钼催化剂的应用与研究进展

为突破铁钼甲醛催化剂“卡脖子”技术,实现其国产化和大面积推广应用,综述了国内外铁钼甲醛催化剂的工业应用、实验室制备和反应及失活机理的研究进展。分析发现,国外铁钼甲醛催化剂经过70年的工业应用与改进,甲醛收率可达93.3%,而国产铁钼甲醛催化剂在开展工业试用后仍未实现大面积的进口替代;共沉淀法是制备该催化剂的主流方法,钼铁比(n(Mo):n(Fe))、助剂种类、沉淀温度、p H值、搅拌速率、陈化时间和煅烧温度等都会影响该催化剂的结构和性能;甲醇在该催化剂上氧化生成甲醛的反应遵循氧化还原机理,晶格氧在其中扮演氧化活性位的角色,甲氧基生成、甲氧基脱氢和晶格氧传递等过程均有可能是反应速控步骤,反应过程中的钼挥发流失是造成该催化剂失活的重要原因。进一步指出国内需针对工业试用出现的问题,加强对铁钼甲醛催化剂形成机制、制备过程对催化剂结构与性能的影响规律和催化反应及失活机理等问题的研究,以提升该催化剂性能,特别是催化剂稳定性。

废石化催化剂微波-超声波协同浸出工艺及动力学研究

研究了采用微波-超声波协同氢氧化钠浸出废石化催化剂中的钒和钼,考察了各因素对浸出率的影响,并分析了浸出过程的动力学。结果表明:在无机械搅拌、固液质量体积比0.20 g/1 mL、浸出温度90℃、氢氧化钠浓度2.0 mol/L、微波功率600 W、超声波功率300 W、浸出时间30 min条件下,废催化剂中V、Mo浸出率分别达95.66%、96.28%;微波-超声波协同浸出的表观活化能为18.80 kJ/mol,较常压浸出大幅降低,这与微波选择性加热特性和超声波的空化作用产生高温高压使得化学键断裂有关。

低温脱硝脱氯苯钒钼钛基催化剂研究——钼负载量的影响

采用浸渍法制备了不同钼负载量的钒钼钛基催化剂,评价了催化剂的脱硝、SO2氧化和脱氯苯的性能,并采用BET、XRD、Py-FTIR、NH3-TPD、NO-TPD和SO_(2)^(-)TPD对催化剂进行了表征。结果显示,催化剂比表面积比较接近,活性组分在TiO2载体表面分散均匀,未发现明显的活性物种XRD衍射峰。吡啶吸附原位红外结果表明,钼的添加增大了表面B酸和L酸位点数目。程序升温脱附表征显示,随着钼负载量的增加,催化剂表面中强酸性位点略有增多,削弱了催化剂对NO和SO_(2)的吸附能力,因此催化剂脱硝和硫氧化性能逐渐减小,脱氯苯的性能有所增加。钼负载量为6wt%时,催化剂的综合脱硝脱氯苯性能较佳。

废旧加氢催化剂中钼回收工艺的研究进展

原油加氢处理消耗了大量的催化剂,这些废旧加氢催化剂中含有大量的钼资源,若直接丢弃,将造成资源浪费和环境污染,因此,从废旧加氢催化剂中回收钼具有重要的意义。综述了从废旧加氢催化剂中回收钼的工艺技术进展,主要讨论了火法、湿法、火湿结合法及其他工艺,并对比了各工艺的优缺点,为后续研究提供思路。

有机钼催化剂前驱体制备单元腐蚀分析与对策

浆态床渣油加氢是目前重油深度加工领域的先进技术,国内某公司已投产了两套3 Mt/a浆态床渣油加氢装置,同时与之配套的有机钼催化剂前驱体制备单元,可实现对这两套装置催化剂的自产供给,该催化剂生产工艺技术以乙酸酐、异辛酸和钼酸为原料,生产出钼质量分数为15%的辛酸钼作为浆态床渣油加氢装置催化剂前驱体,同时副产乙酸,工艺系统腐蚀环境较为复杂,在催化剂生产过程中,催化剂前驱体制备单元频繁出现腐蚀泄漏问题。该文主要介绍了催化剂生产过程中出现的腐蚀案例,同时对腐蚀问题进行分析,并探讨相应的防腐对策。