Facile molybdenum and aluminum recovery from spent hydrogenation catalyst

Industrial catalyst waste has emerged as a hazardous pollutant that requires safe and proper disposal after the unloading process.Finding a valuable and sustainable strategy for its treatment is a significant challenge compared to traditional methods.In this study,we present a facile method for the recovery of molybdenum and aluminum contents from spent Mo-Ni/Al_(2)O_(3) hydrogenation catalysts through crystallization separation and coprecipitation.Furthermore,the recovered molybdenum and aluminum are utilized as active metals and carriers for the preparation of new catalysts.Their properties were thoroughly analyzed and investigated using various characterization techniques.The hydrogenation activity of these newly prepared catalysts was evaluated on a fixed-bed small-scale device and compared with a reference catalyst synthesized from commercial raw reagents.Finally,the hydrogenation activity of the catalysts was further assessed by using the entire distillate oil of coal liquefaction as the raw oil,specifically focusing on denitrogenation and aromatic saturation.This work not only offers an effective solution for recycling catalysts but also promotes sustainable development.

Microwave Plasma Treatment for Catalyst Preparation: Application to Alumina Supported Silver Catalysts for SCR NO_xby Ethanol

Thermal treatment either in the presence of oxygen (calcination) or of a reducing agent (reduction) result is all the time a key issue within the preparation of a catalyst. In this work, a microwave plasma treatment was chosen as an alternative to typical calcinations, because it is a more energy efficient process. Thus, a Microwave Fluidized Bed Plasma reactor (MFBP) was employed in catalyst synthesis process under different gas compositions, such as argon and argon/oxygen mixtures over g-alumina supported silver catalysts, which are generally used for selective reduction of NOx by ethanol. After the first catalytic tests performed in the presence of plasma treated catalyst, it can be concluded that plasma treatment process represents an interesting alternative to conventional calcination during catalyst synthesis, resulting in a more sustainable process, moreover in view of its industrial application. In order to understand the particular effect of plasma treatment, the catalysts submitted to this treatment were carefully characterized by means of thermo gravimetric analysis (TGA), differential thermal analysis (DTA) and UV-VIS-NIR.

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.

Hydrothermal treatment of metallic-monolith catalyst support with self-growing porous anodic-alumina film

Metallic-monolith catalyst support with self-growing porous anodic alumina(PAA)film was prepared by anodizing Al plate.The effect of hydrothermal treatment(HTT)on the crystalline state and textural properties of PAA film was investigated by XRD,BET,SEM and TG.The HTT treatment above 50°C and the subsequent calcination above 300°C could convert the amorphous skeleton alumina intoγ-alumina and increase the specific surface area(SBET).However,SEM images showed the HTT modification was a non-uniform process along the thickness of PAA film.The promotion effect of HTT on SBETwas non-linear,and the slope of SBETgradually decreased with the HTT temperature or time increased.The limited HTT effect should be attributed to a changed pore structure caused by an unfavorable pore sealing limitation.Pore widening treatment(PWT)before HTT could break the pore sealing limitation,because of the reduced internal diffusion resistance of hydrothermal reaction.The synergistic combination of PWT and HTT developed a PAA support with a large SBETcomparable to commercialγ-alumina.In the catalytic combustion of toluene,the Pt-based catalyst prepared by using the PWT and HTT comodified PAA support gave higher Pt dispersion and more favorable catalytic activity than that treated by HTT alone.The presence of a bimodal pore structure was suggested to be a decisive reason.

Synthesis and characterization of multiwall carbon nanotubes/alumina nanohybrid-supported cobalt catalyst in Fischer-Tropsch synthesis

Multiwall carbon nanotubes （MWNTs） and alumina are combined to give a new type of nanohybrid for Fisher-Tropsch synthesis （FTS） catalyst support. Alumina nano-particles （10 wt%） were introduced directly on functionalized MWNTs by a modified sol-gel method. Microstructure observations show that alumina particles were homogeneously dispersed on the inside and outside of modified MWNTs surfaces. 15 wt% cobalt loading catalysts were prepared with this nanohybrid and γ-alumina as a reference, using a sol-gel technique and wet impregnation method respectively. These catalysts were characterized by TEM, XRD, N2-adsorption, H2 chemisorption and TPR. The deposition of cobalt nanoparticles synthesized by sol-gel technique on the MWNTs nanohybrid shift the reduction peaks to a low temperature, indicating higher reducibility for uniform cobalt particles. Nanohybrid also aided in high dispersion of metal clusters and high stability and performance of catalyst. The proposed MWNTs nanohybrid-supported cobalt catalysts showed the improved FTS rate （gHc/（gcat.min））, CO conversion （%）, and water gas shift rate （WGS）（gcoz/（gcat.h）） of 0.012, 52, and 30E-3, respectively, as compared to those of 0.007, 25, and 18E-3, respectively, on the γ-alumina-supported cobalt catalysts with the same Co loading.

Influence of Pretreatment on the Interaction of Oxygen with Silver and the Catalytic Activity of Ag/SiO_(2) Catalysts for CO Selective Oxidation in H_(2)

The interactions of oxygen with pre-reduced silver catalysts as well as theircatalytic properties for CO selective oxidation in H_2 after oxygen pre-treatment are studied inthis paper. It is found that the pretreatment exerts a strong influence on the activity andselectivity of the silver catalyst. A drop in activity and selectivity is observed after treating apre-reduced catalyst with oxygen at low temperatures, whereas a converse result is obtained after anoxidizing treatment at high temperatures (T ≥ 350℃). O_2-TPD results show that surface oxygenspecies adsorbs on silver surface after the oxygen treatment at low temperatures. However,penetration of oxygen into the silver is enhanced by a high temperature treatment, meanwhile thesurface oxygen species disappear. No other silver species except metallic silver are observed on allthe catalysts by XRD, and the size of silver particle is not changed after the treatment withoxygen at low temperatures. The surface oxygen species formed by oxygen treatment can also beremoved by hydrogen reduction. The strongly-adsorbed surface oxygen species prohibit the adsorptionand diffusion of oxygen species in reaction gas on the surface of silver catalyst, causing thedecrease in CO oxidation activity, in other words, it is important to obtain a clean silver surfacefor increasing the catalyst activity in CO removal from H_2-rich feed gas. The differences inactivity and selectivity due to the oxygen pretreatment at different temperatures are discussed interms of the changes in the surface/subsurface oxygen species of the silver particles.

Solvent-free synthesis of alumina supported cobalt catalysts for Fischer–Tropsch synthesis

A novel mechano-synthesis method has been elaborated in this work for the design of efficient cobalt-based Fischer–Tropsch catalysts. The process aims to reduce the total number of steps involved in the synthesis of solid catalysts and thus to avoid relevant toxic solutions generated during the catalyst preparation. The mechano-synthesis of the Co/Al2O3catalyst was processed in a low-energy vibratory micro mill and high energy planetary ball mill. Porous spherical γ-aluminas (1860 µm and 71 µm mean particle diameter) were used in this work as host compounds. Co3O4(3 µm mean particle diameter) has provided guest particles for mechano-synthesis. The catalysts were characterized by textural (surface area, porosity and particle size) and structural analyses (X-ray diffraction, TPR, SEM-EDX and microprobe). The microprobe images show deposition of Co3O4on the surface of the alumina and indicated no Co3O4diffusion inside the alumina pores. SEM-EDX mapping illustrated that cobalt coating tended to occur on surface of rounded shape of cracked alumina fragments. After milling, the crystallite size of Co3O4decreased to 15 nm from 30 to 50 nm. The TPR profiles indicated very low concentrations of inactive cobalt aluminate mixed compounds which are usually produced during the catalyst preparation by impregnation. In Fischer–Tropsch synthesis, the catalysts prepared using mechano-synthesis methods showed catalytic performance comparable to the catalysts prepared by impregnation. © 2016 Science Press

Fischer-Tropsch Synthesis over Alumina- Supported Cobalt-Based Catalysts: Effect of Support Variables

Different kinds of aluminum precursors were obtained from precipitating ammonium bicarbonate, ammonium carbonate, and saturated ammonium bicarbonate, then, boehmite (AlO(OH)), ammonium alumina carbonate hydroxide (AACH) and their mixture were obtained, and then, different kinds of alumina were obtained after calcination. Three catalysts supported on the different alumina were obtained via impregnating cobalt and ruthenium by incipient wetness. The effects of different precipitants on composition of precursors were?studied by XRD, FTIR, and TGA. The property and structure of alumina were studied by XRD and BET. The supported catalysts were studied by characterizations of XRD and H2-TPR, and the catalytic performance for Fischer-Tropsch synthesis (FTS) were evaluated at a fix-bed reactor. The relations among the composition of precursors, the property of alumina and the catalytic performance of supported catalysts were researched thoroughly.

Preparation of Alumina Abrasion-Resistant Ceramic Grinding Ball with Spent FCC Equilibrium Catalyst

化学作文，结构和从一个炼油厂的花的 FCC 平衡催化剂的热稳定性被 XRD，英尺红外， DTA-TG，赌注，完全的化学分析， SEM，和 XRF 描绘。花的 FCC 平衡催化剂，泥土，钡碳酸盐，和滑石被用作主要原料准备氧化铝在为建筑学瓦的制造磨工厂的粉末要过去常的磨损抵抗的陶器的球。结果证明在合适的明确的表达学习以后，花的 FCC 平衡催化剂能代替工业氧化铝准备磨球的高效。同时，磨擦的球的各种各样的表演索引能为类似的产品满足优秀标准，并且另外，节省效果的精力在磨擦的节的操作被完成，导致稳固的浪费的成功的全面利用。

Simultaneous operation of dibenzothiophene hydrodesulfurization and methanol reforming reactions over Pd promoted alumina based catalysts

In the current study simultaneous reactions of hydrodesulfurization(HDS) of dibenzothiophene(DBT) and reforming of methanol in a micro-autoclave reactor were studied over bi-metallic(Co-Mo/Al2O3 and Ni-Mo/Al2O3) and tri-metallic(Pd-Co-Mo/Al2O3 and Pd-Ni-Mo/Al2O3) catalyst systems which were prepared by incipient impregnation method.In situ hydrogen utilization and low Pd loadings were the major targets of this study.For comparison purpose,catalytic activity was separately determined for both the methanol reforming and HDS of DBT reactions as well.Ni based catalysts were confirmed with better activity than Co ones for both the reactions with Pd promoted ones ranking at the top i.e.Pd-Ni-Mo/Al2O3 > Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3 > Co-Mo/Al2O3 where Pd-Ni-Mo/Al2O3 showed 91% DBT conversion at 380 ℃ and 12 h reaction time.Some of the selected organic additives on catalytic activity were tested for their effect toward HDS reaction which was unique with close relation to their chemical nature.Reaction products were quantitatively and qualitatively analyzed via HPLC and GC-MS techniques respectively which helped in elucidating reaction mechanism.

Cobalt supported on CNTs-covered γ-and nano-structured alumina catalysts utilized for wax selective Fischer-Tropsch synthesis

Cobalt supported on carbon nanotubes （CNTs）-covered alumina has been recently developed and successfully utilized as a catalyst in Fischer-Tropsch synthesis （FTS）. Problems associated with shaping of Co/CNTs into extrudates or pellets as well as catalyst attrition rendered these materials unfavorable for industrial applications. In this investigation regular γ- and nano-structured （N-S） alumina as well as CNTs-covered regular γ- and N-S-alumina supports were impregnated by cobalt nitrate solution to make new cobalt-based catalysts which were also promoted by Ru. The catalysts were characterized and tested in a micro reactor to evaluate their applicability in FTS. γ-Al2O3 was prepared by calcination of bohemite and N-S-Al2O3 was prepared by sol-gel method using aluminum chloride as starting material. Catalyst evaluations indicated that N-S-Al2O3 was superior to regular γ-Al2O3 and that CNTs-covered alumina supports were favored over non-covered ones in terms of activity and heavy hydrocarbon selectivity. These were justified by porosimetric characteristics of the catalysts and existence of CNTs points of view. CNTs-covered catalysts also showed higher wax selectivity and better resistance to deactivation. Furthermore, TPR analysis indicated that the cobalt aluminate phase, which is responsible for the permanent deactivation of alumina supported Co-based catalysts, did not form on alumina supported Co-based catalysts covered with CNTs due to weaker interactions between cobalt and alumina.

Methane Dry Reforming over Alumina Supported Co Catalysts

A series of Co/γ-Al_2O_3 catalysts were prepared with the impregnation method and characterized by means of the BET specific surface area, X-ray diffraction(XRD), thermogravimetric analysis(TGA) and Laser Raman spectroscopy. The Co/γ-Al_2O_3 catalysts were activated by using H_2, 20%CH_4/H_2 or CH_4, respectively. There was no obvious difference between the activities of the Co/γ-Al_2O_3 catalyst activated by using the different activation methods for methane dry reforming. The catalytic properties of the Co/γ-Al_2O_3 catalysts with different Co loadings were also investigated. The optimized Co loading for the Co/γ-Al_2O_3 catalyst pretreated with 20% CH_4/H_2 is around 12%(mass fraction).

Adsorption of gaseous iodine-131 at high temperatures by silver impregnated alumina

To prevent radioactive iodides from releasing into the environment in an accident of a nuclear power plant,silver-impregnated alumina(Ag/Al2O3)was fabricated,and its performance of radioactive iodine adsorption from high-temperature gas was tested.The silver loadings on alumina were obtained by ICP-OES and the texture properties of Ag/Al2O3were characterized by N2adsorption-desorption.The Ag/Al2O3was of reduced specific surface(107.2 m2/g at 650?C).Crystalline phases of Ag/Al2O3were confirmed through XRD characterization.After calcination at 650?C for 2 h,the crystalline phase of Ag/Al2O3changed.The131I-removal efficiency of Ag/Al2O3was tested at 100,250,350,450 and 650?C,with good decontamination factor values for the radioactive iodine.Silver-impregnated alumina can be applied as adsorbents to remove radioactive iodine at high temperatures in nuclear accident.

Macrokinetics of Ethylene Epoxidation over A-type Silver Catalyst

By taking the surface chemical reactions as the rate-controlling step, a possible reaction mechanism for ethylene epoxidation to synthesize ethylene oxide over the A-type silver catalyst was developed, while it was assumed that the epoxidation reaction would take place between ethylene and the un-dissociated adsorbed oxygen O2 a on the solo active sites, while the deep oxidation would occur between ethylene and the dissociated adsorbed oxygen Oa on the adjacent multi-active sites. In order to describe the effect of 1,2-C2H4Cl2(EDC) inhibitor on the ethylene epoxidation process, the reversible reactions between EDC and vinyl chloride(VC) on the active sites of silver catalyst was introduced. According to the assumed mechanism, the hyperbolic macro-kinetic model of ethylene epoxidation over the A-type silver catalyst was established, and the macrokinetic experiments were carried out in an internal-recycle gradientless reactor operating at a pressure of 2.1 MPa and a temperature in the range of 217.8—249.0 ℃, with the gas composition(molar fraction) consisting of 15.82%—34.65% C2H4, 2.55%—7.80% O2, 0.88%—6.15% CO2, 0.15—2.61 μmol/mol of 1,2-C2H4Cl2 and 0.14—1.28 μmol/mol of C2H3 Cl. By means of the Simplex Optimal Method, the parameters of the macrokinetic models were estimated. Statistical test showed that the macrokinetic models developed for the A-type silver catalyst agree well with the experimental results.

An Experimental Study of the Performance of Isomorphically Zirconium-Substituted Mesoporous Alumina Supported Cobalt Catalysts in Fischer-Tropsch Synthesis

A series of mesoporous alumina (MA) supported cobalt (Co/MA) catalysts with MA isomorphically substituted by zirconium (Zr) were synthesised and evaluated for their performance in the Fischer-Tropsch synthesis. The Zr/(Zr + Al) atomic ratios varied from 1% - 15%. A zirconium-impregnated Co/MA catalyst prepared by wet impregnation with a Zr/(Zr + Al) atomic ratio of 5% was also evaluated to examine Zr incorporation’s effect method. The catalysts synthesised were characterised using N2 adsorption-desorption, X-ray Powder Diffraction (XRD), Transmission Electron Microscopy (TEM), and X-Ray Photoelectron Spectroscopy (XPS). It was found that Zr4+ ions were incorporated into the framework of MA and kept intact up to a Zr/(Zr + Al) atomic ratio of 5%. The cobalt dispersion and reducibility were improved as the Zr/(Zr + Al) atomic ratio increased to 50%. The performance of these catalysts for Fischer-Tropsch synthesis was evaluated using a fixed bed reactor at temperature and pressure of 493 K and 20 bar, respectively. The feed syngas had an H2/CO ratio of 2, diluted with 10% Ar. For isomorphically Zr-substituted Co/MA, the CO conversion and selectivity of diesel (C10 - C20) increased first and then decreased with increasing the Zr/(Zr + Al) atomic ratio. The maximum 38.9% CO conversion and 34.6% diesel (C10 - C20) selectivity were obtained at Zr/(Zr + Al) atomic ratio of 5%. The isomorphic substitution method was better than the wet impregnation method in CO conversion and diesel selectivity.

小晶粒高硅铝比NaY分子筛低温合成研究

采用自制的偏铝酸钠为合成导向剂,在低温下水热晶化合成出了小晶粒高硅铝比的NaY分子筛。考察了合成导向剂的陈化温度、陈化时间、晶化碱度、晶化温度和晶化时间对产品的影响,得到了制备NaY分子筛最佳的工艺条件,并进行了放大制备。在此条件下,NaY分子筛结晶度(峰面积)≥90%,结晶度(峰高)≥85%,硅铝比≥5.5,晶粒尺寸均在(100~200)nm,不仅优于工业标样的指标要求,且易于放大。

氧化铝结构与表面性质调控及其催化甲醇脱水制二甲醚性能研究

二甲醚(DME)作为一种关键的化工原料,被广泛用于合成众多重要的化学品及能源产品。在工业生产中用于从甲醇制备DME的催化剂γ-Al_(2)O_(3)因其高效的催化性能而得到普遍应用。然而,γ-Al_(2)O_(3)的合成方法和制备条件对其催化性能有着显著的影响。目前,对于工业上常用的γ-Al_(2)O_(3)合成条件如何影响其催化性能的系统研究仍然不足。特别是,作为影响催化性能的关键因素之一,酸性位点的性质尚未形成共识。通过调控双铝法成胶过程中母液的pH,成功合成了一系列具有不同孔道结构和酸性质的γ-Al_(2)O_(3)。实验结果表明,随着母液pH的增大,γ-Al_(2)O_(3)的比表面积、孔容和孔径均呈现减小趋势。同时,γ-Al_(2)O_(3)的弱酸量逐渐减小,而中强酸量呈现先增后减的趋势。进一步结合催化性能评估结果,发现中强酸数量与甲醇脱水性能密切相关。具有最高中强酸数量的γ-Al_(2)O_(3)表现出最高的DME产率,预示中强酸位点是γ-Al_(2)O_(3)催化甲醇脱水制备DME的主要活性中心。针对具有最优性能的γ-Al_(2)O_(3)开展动力学实验分析,得到甲醇脱水的反应级数为0.78,反应活化能为83.27 kJ/mol。研究可为甲醇脱水制备DME催化剂的设计提供指导,为进一步优化工业生产条件和提高催化效率夯实基础。

Al/SO_(4)^(2-)复合改性CrO_(x)/VO_(x)/SiO_(2)双金属催化剂及其乙烯聚合特性研究

采用溶液浸渍及高温煅烧的方法制备了一系列Al/SO_(4)^(2-)复合改性CrO_(x)/VO_(x)/SiO_(2)双金属催化剂,并研究了其催化乙烯聚合特性。结果表明:采用较低的m(Al)∶m(S)改性的双金属催化剂活性较未改性催化剂提升20%~40%;改性前后催化剂均表现出稳定的聚合活性,采用改性催化剂制备的聚合物相对分子质量更高,相对分子质量分布更宽;采用改性前后催化剂制备的聚合物相对分子质量分布均呈双峰,采用改性催化剂时其超高相对分子质量部分含量有所增加,而中、高相对分子质量部分含量明显更少。上述结果为单釜高效合成双峰聚乙烯产品及聚合物相对分子质量调控提供了重要手段。

乙烯环氧化反应及催化剂改性研究进展

乙烯环氧化反应的性能决定了环氧乙烷装置的经济性,而银催化剂是乙烯环氧化反应的主要工业催化剂。介绍了乙烯环氧化反应的研究现状,分析了影响银催化剂乙烯环氧化反应性能的因素,综述了银催化剂的改性方法,包括载体改性、活性中心调控和助催化体系优化等对催化性能的影响,并对进一步研究提出了建议。

制备方法对碳烟催化中Ag-Cs协同体系影响研究

采用离子交换法和浸渍法分别合成了Ag-Cs/ZSM-5(E)和Ag-Cs/ZSM-5(D)双金属催化剂.利用X射线衍射光谱(XRD)、X射线光电子能谱(XPS)、透射电镜(TEM)等手段表征材料的物理、化学状态.通过程序升温氧化(TPO)测试催化剂活性,发现在氧气气氛下,Ag-Cs/ZSM-5(E)和Ag-Cs/ZSM-5(D)双金属催化剂催化活性较Ag/ZSM-5有着非常明显的提升,T50从Ag/ZSM-5的546℃分别降低至Ag-Cs/ZSM-5(E)的430℃和Ag-Cs/ZSM-5(D)的464.℃同时,Ag-Cs/ZSM-5(E)比Ag-Cs/ZSM-5(D)表现出更佳的催化活性和稳定性.研究结果证实了Ag-Cs双金属的协同作用,以及ZSM-5载体上路易斯酸性位点Cs在双金属协同中的关键作用.