氢气氛下半焦有机硫的脱除动力学

研究了半焦颗粒在氢气氛下有机硫脱除的本征动力学行为.实验采用微分反应器,研究结果表明,半焦颗粒的脱硫与气氛、温度和半焦硫含量有关.通过比较粒子反应模型和随机孔模型,粒子反应模型仅适合于处理半焦颗粒氢气气氛脱硫的初始阶段,而随机孔模型符合整个脱硫过程.实验和理论分析揭示了脱硫过程中煤中有机硫形态的转化.     

Effects of preparation conditions in hydrothermal synthesis of highly active unsupported NiMo sulfide catalysts for simultaneous hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene

Unsupported NiMo sulfide catalysts were prepared from ammonium tetrathiomolybdate (ATTM) and nickel nitrate by using a hydrothermal synthesis method involving water, organic solvent and hydrogen. The activity of these catalysts in the simultaneous hydrodesulfurization (HDS) of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was much higher than that of the commercial NiMo/Al₂O₃ sulfide catalysts. Interestingly, the unsupported NiMo sulfide catalysts showed higher activity for hydrogenation (HYD) pathway than the direct desulfurization (DDS) pathway in the HDS of DBT. The same trends were observed for the HDS of 4,6-DMDBT. Morphology, surface area, pore volume and the HDS activity of unsupported NiMo sulfide catalyst depended on the catalyst preparation conditions. Higher temperature and higher H₂ pressure and addition of an organic solvent were found to increase the HDS activity of unsupported NiMo sulfide catalysts for both DBT and 4,6-DMDBT HDS. Higher preparation temperature increased HYD selectivity but decreased DDS selectivity. High-resolution TEM images revealed that unsupported NiMo sulfide prepared at 375 °C shows lower number of layers in the stacks of catalyst with more curvature and shorter length of slabs compared to that prepared at 300 °C. On the other hand, higher preparation pressure increased DDS selectivity but decreased HYD selectivity for HDS of 4,6-DMDBT. HRTEM images showed higher number of layers in the stack for the NiMo sulfide prepared under an initial H₂ pressure of 3.4 MPa compared to that under 2.1 MPa. The optimal Ni/(Mo + Ni) ratio for the NiMo sulfide catalyst was 0.5, higher than that for the conventional Al₂O₃-supported NiMo sulfide catalysts. This was attributed to the high dispersion of the active species and more active NiMoS generated. The present study also provides new insight for controlling the catalyst selectivity as well as activity by tailoring the hydrothermal preparation conditions.     

Elucidation of hydrogen mobility in coal under reductive atmosphere using a tritium tracer method

Hydrogen exchange reaction of three Argonne coals (Illinois No. 6, Upper Freeport and Pocahontas #3) and Wandoan coal with tritiated gaseous hydrogen were performed at several temperatures. Hydrogen exchange reaction was performed in a flow reactor packed with 0.4 g of coal and 0.05 g of catalysts under the following conditions: pressure 15 kg/cm², temperature 200, 250, 300 °C, carrier gas H₂ or N₂ 5 ml/min. When a pulse of [³H]H₂ was introduced into a coal in H₂ carrier gas at several temperatures, the delay of [³H]H₂ pulse observed increased with increasing the reaction temperature and decreased with increasing coal rank. Further in the reaction of tritiated coals with gaseous hydrogen at constant temperature, the hydrogen exchange rate was estimated from the release rate of [³H]H₂. The apparent hydrogen exchange rate at 200 °C was higher than that at 250 °C. This shows that the hydrogen with low reactivity came to participate in the reaction at high temperature. When the reaction of tritiated coal with gaseous hydrogen was performed during heat treatment, one, two or three peaks of tritium concentration were observed in the outlet of the reactor depending on temperature (200, 250 or 300 °C, respectively) at which tritium was incorporated into coal initially. It was suggested that there were at least three kinds of hydrogen with different reactivity in coal.     

CCSEM analysis of ash from combustion of coal added with limestone

Combustion of three Chinese coals, mixed with limestone physically, was carried out in drop tube furnace. The drop tube furnace consisted of two parts, the top side has a length of about 1.0 m and kept at 1573 K in all the runs, while the bottom-side has a length of 0.5 m and kept at 1173 K. SO₂ removal efficiency of about 80 and 73% were obtained in the combustion of Yanzhou with high and low sulfur, respectively. In contrast, for Datong coal, the De-S efficiency was only about 50% at the molar Ca/S ratio of 2.0; increasing Ca/S ratio to 3.0 had little effect on De-S efficiency. The combustion ashes were analyzed by several techniques including XRD, SEM-EDX and CCSEM (computer-controlled SEM). A novel calcium-based phase definition, based on CCSEM data was developed to investigate the modes of occurrence of added limestone in the ashes. Additionally, the mixture of limestone with kaolinite was injected into the furnace to study their transformation behavior under simulated coal combustion conditions. The governing mechanisms for limestone capturing sulfur and its reaction with the inherited minerals were correspondingly revealed. It was found that under the given coal combustion conditions, the calcium distribution in the ash varied with coal type and residence time. Briefly, more calcium was used for desulfurization or fixed into mineral; as time progressed, the inherited aluminosilicate, small sized excluded particles in the coal matrix, facilitated its reaction with limestone; it also reacted quickly compared to sulfation of limestone in coal combustion. This in turn hampered the efficient utilization of limestone in coal combustion.     

Phase-controlled solvothermal synthesis and morphology evolution of nickel sulfide and its pseudocapacitance performance

Phase-controlled solvothermal synthesis has been proposed for the synthesis of nickel sulfide of single phase including α-NiS, Ni₃S₄ and NiS₂ by tuning the reaction time and the addition of surfactant. The phase evolution of nickel sulfide proceeds with the increase of sulfur stoichiometry with longer reaction time in the presence of surfactant. With the addition of hexadecyl-trimethyl-ammonium bromide (CTAB), a higher sulfur stoichiometry NiS₂ phase with hollow sphere geometry was synthesized at 9 h, a much shorter time due to the enrichment of S²⁻ on CTAB micelle surface, followed by the transformation to single phase Ni₃S₄ finally due to dissipation of enriched sulfur to the bulk solution. The application of these three single phase materials in supercapacitors was investigated. The α-NiS electrode material outperformed the Ni₃S₄ and NiS₂ electrodes, exhibiting a much higher specific capacitance of 800 F g⁻¹ at 0.5 A g⁻¹, attributable to the small particle size, high electrical conductivity and the unique hexagonal crystal structure.     

Ultra-deep oxidative desulfurization of diesel fuel by the Mo/Al2O3-H2O2 system: The effect of system parameters on catalytic activity

This work presents the results obtained in the development of Mo/γ-Al₂O₃ catalysts and their evaluation in the oxidative desulfurization (OD) process of diesel fuel using hydrogen peroxide as the oxidizing reagent. The catalysts were prepared by equilibrium adsorption using several molybdenum precursors and aluminas with different acidity values. They were characterized by Raman spectroscopy. The effect of the reaction time, reaction temperature, nature of solvent, concentration of solvent and hydrogen peroxide, content of molybdenum and phosphate in the catalysts were investigated. The results showed that the activity for sulfur elimination depends mainly on the presence of hepta- and octamolybdates species on the catalyst support and the use of a polar aprotic solvent. Likewise, the presence of phosphate markedly increases the sulfur elimination. In this way, it is possible to reduce sulfur level in diesel fuel from about 320 to less than 10 ppmw at 333 K and atmospheric pressure. Additionally, on the basis of the results obtained a mechanistic proposal for this reaction is described, as an oxidation mechanism by nucleophilic attack of the sulfur atom on peroxo species of hepta- and octamolybdates, but a mechanism involving the singlet oxygen presence can be discarded.     

Nanostructured nickel ferrite: A liquid petroleum gas sensor

The present investigation deals with the synthesis of nanostructured nickel ferrite (NiFe₂O₄) and their liquid petroleum gas-sensing characteristics. The 15–20 nm size nickel ferrite has been synthesized at 700 °C by a simple molten-salt route using sodium chloride as grain growth inhibitor. These nanoparticles exhibit significantly high response towards liquid petroleum gas (LPG) in comparison with ethanol vapor, hydrogen sulfide, ammonia and hydrogen. The gas response towards various gases at their 200 ppm concentrations is investigated at 200–450 °C. Different characterization techniques have been employed, such as differential thermal analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM) to study the crystallite size, structure and morphology. The results suggest possibility of utilization of the nanostructured nickel ferrite, without addition of any precious metal ion, as the LPG detector.     

Enhanced blue-light photocatalytic H2 production using CdS nanofiber

The photocatalytic activity of CdS nanosphere, nanorod or nanofiber was investigated for the hydrogen production from either methanol–water or sulfide/sulfite solution irradiated with blue light. The nanostructured CdS were obtained by the precipitation method at high ethylenediamine content solutions and at moderate temperature conditions. The synthesized CdS nanofiber using CS₂ as sulfur source presented the highest photocatalytic activity for the H₂ production (954 μmol h^− 1 g^− 1) in the reaction system with four blue LED lamps. This high photoactivity was attributed to the quantum confinement effect generated by the small particle size of the nanofibers (D = ~ 5 nm and L = 25 nm).     

Deep oxidative desulfurization of model fuel using ozone generated by dielectric barrier discharge plasma combined with ionic liquid extraction

The dielectric barrier discharge (DBD) is often used to prepare ozone. In this study, a novel room temperature oxidative desulfurization method involving ozone oxidation produced in the DBD reactor combined with ionic liquid (IL) [BMIM]CH₃COO ([BMIM]Ac) extraction was developed. The method was suitable for the deep removal of sulfur (S)-containing compounds from model fuel. By this desulfurization technology, 4,6-dimethyldibenzothiophene (4,6-DMDBT), dibenzothiophene (DBT), benzothiophene (BT) and thiophene (TS) were efficiently removed. Normally, the removal of TS and BT from fuel is highly difficult. However, using the proposed method of this study without any catalyst, the removal rate of TS and BT reached 99.9%. When TiO₂/MCM-41 was used as a catalyst, the S-removal of DBT and 4,6-DMDBT increased to 98.6 and 95.2%, respectively. The sulfur removal activity of the four sulfur compounds decreased in the order of TS > BT >> DBT > 4,6-DMDBT.     

Catalytic conversion of CO,NO and SO2 on the supported sulfide catalyst: I. Catalytic reduction of SO2 by CO

Catalytic reduction of SO₂ to elemental sulfur by CO has been systematically investigated over γ-Al₂O₃-supported sulfide catalysts of transition metals including Co, Mo, Fe, CoMo and FeMo with different loadings of the metals. The sulfided CoMo/Al₂O₃ exhibited outstanding activity: a complete conversion of SO₂ was achieved at a temperature of 300°C. The reaction proceeds catalytically and consistently over time and most efficiently at a molar feed ratio CO/SO₂ = 2. A precursor CoMo/Al₂O₃ oxide which experienced sulfurization through the CO–SO₂ reaction yielded a working sulfide catalyst having a yet lower activity than the CoMo catalyst sulfided before reaction (pre-sulfiding). The catalytic activity of various metal sulfides decreased in order of 4% Co 16% Mo > 4% Fe15% Mo > 16% Mo ≥ 25% Mo > 14% Co ≥ 4% Co > 4% Fe. A DRIFT study showed that CO adsorbs exclusively on CoMo phase and that SO₂ predominantly on γ-Al₂O₃. It is suggested that the Co–Mo–S structure is more adequate than the other metal-sulfur structures for the formation of a carbonyl sulfide (COS) intermediate because of the proper strength of metal–sulfur bond, and catalytically works with γ-Al₂O₃ for the COS–SO₂ reaction.     

Analysis and removal of heteroatom containing species in coal liquid distillate over NiMo catalysts

Heteroatom containing molecules in South Banko coal liquid (SBCL) distillate were identified with a gas chromatograph equipped with an atomic emission detector (GC-AED). Thiophenes and benzothiophenes were found to be the major sulfur compounds. Pyridines, anilines, and phenols were the major nitrogen and oxygen compounds, respectively. Reactivities of heteroatom containing species in hydrotreatment over conventional NiMoS/Al₂O₃, NiMoS/Al₂O₃–SiO₂ catalysts were very different according to their cyclic structure as well as the kind of heteroatom in the species. The sulfur species were completely desulfurized over the catalysts examined in the present study by 60 min at 360 °C under initial hydrogen pressure of 5 MPa. However, hydrodenitrogenation was more difficult than hydrodesulfurization even at 450 °C. Anilines were found the most refractory ones among the nitrogen species. Hydrodeoxygenation of SBCL was also difficult in the hydrotreatment conditions examined in the present study. Dibenzofuran was the most refractory molecule among the oxygen species. A two-stage reaction configuration at 340 and 360 °C improved HDN and HDO reactivities, although the conversions were still insufficient. Increasing the acidity of the support as well as the loading of the metals on the NiMoS/Al₂O₃ catalysts improved very much the heteroatom reduction to achieve complete removal of nitrogen by two-stage reaction configuration at 340–360 °C and oxygen at 360 °C, respectively. The addition of H₂S in the reaction atmosphere inhibited the HDN reaction but increased markedly the HDO conversion. The acidic support increased the activity in hydrotreatment through enhancing the hydrogenation activity, while H₂S maintained the catalyst in a sufficiently sulfided state.     

Hydrodesulfurization of diesel in a slurry reactor

The need for more complete removal of sulfur from fuels is due to the lower allowable sulfur content in gasoline and diesel, which is made difficult by the increased sulfur contents of crude oils. This work reports an experimental study on the hydrodesulfurization (HDS) of diesel in a slurry reactor. HDS of straight-run diesel using a NiMoS/Al₂O₃ catalyst was studied in a high-pressure autoclave for the following operating conditions: 4.8–23.1 wt% catalyst in the reactor, 320–360 °C, 3–5 MPa pressure, and 0.56–2.77 L/min hydrogen flow rate. It was found that the reaction rate was proportional to the catalyst amount and increased with temperature, pressure and hydrogen flow rate. The reaction kinetics for the HDS reaction in the slurry reactor was obtained. As compared with HDS in a fixed bed reactor, HDS in a slurry reactor is promising because of the uniform temperature profile, high catalyst efficiency, and online removal and addition of catalyst.     

Properties of high ash coal-char particles derived from inertinite-rich coal: II. Gasification kinetics with carbon dioxide

The reaction rate of carbon dioxide-nitrogen gas mixtures with a well-characterised high ash char derived from an inertinite-rich coal discard was investigated by experimentation and reaction rate modelling. Experimentation with a thermogravimetric analyzer at 87.5 kPa and 287.5 kPa between 850 °C and 900 °C and with 1mm diameter particles, similar to operating conditions used for bubbling fluidised bed gasification, was carried out. The char consisted of a large proportion of dense char formed from the inertinite in the parent coal, fine pores from the low concentration of reactive macerals and cracks formed as a result of thermal deflagration. The effects of carbon dioxide concentration, temperature and pressure on the carbon conversion with time were found to follow expected trends with long reaction times. The random pore model, which accounts for intraparticle structural changes, was examined to predict the overall reaction rate. For this evaluation, a new procedure was developed to determine the structural parameter which could not be calculated directly from initial characterisation results. This procedure consists of defining a reduced time parameter, which conveniently eliminates the effect of the intrinsic kinetics when conversion versus the reduced time results is used. Thus, the structural parameter, which characterises the pore growth and coalescence, can be evaluated by a regression procedure using experimental results obtained at all temperatures and pressures. Intrinsic reaction parameters based on the power rate law were also calculated from carbon conversion versus real time results using a stepwise regression procedure. It was found that the random pore model predictions for the carbon conversion with time using the determined parameters correlated very well with experimental results, thus confirming that the reaction rate is chemical-reaction controlled.     

One-pot synthesis of nickel sulfide with sulfur powder as sulfur source in solution and their electrochemical properties for hydrogen evolution reaction

Among low-cost and earth-abundant elements, the nickel-based HER catalysts, particularly nickel sulfide, are considered as one of the most promising candidates in this field. In this paper, a kind of spherical nickel sulfide material was obtained using nickel acetate and sulfur powder as precursors by one-pot synthesis. The use of sulfur powder as sulfur source with solution-based method will enable the synthesis of metal sulfides to be more simple and capable of mass production. In addition, the as-synthesized nickel sulfide exhibits an onset overpotential of as low as 25 mV, a Tafel slope of 90 mV dec^− 1, and an exchange current density of 0.44 mA cm^− 2. Furthermore, this catalyst maintains its catalytic activity for at least 25 h and only requires overpotentials of 42 and 113 mV to attain current densities of 2 and 10 mA cm^− 2, respectively. The electrocatalytic performance is promising for applications as non-noble-metal HER catalyst with water splitting for hydrogen production.     

Preparation of phosphate promoted Na2WO4/Al2O3 catalyst and its application for oxidative desulfurization

Phosphate promoted Na₂WO₄/Al₂O₃ catalyst with 10 wt.% tungsten was prepared by simple impregnation method. Analytical characterization results showed that tungstate and phosphate were uniformly dispersed in alumina matrix and its structural properties were preserved. The effect of phosphate as promoter in catalyst activity was studied using dibenzothiophine (DBT) as model oil and the results reveal that it plays an important role in oxidation activity of Na₂WO₄/Al₂O₃ catalyst, in addition, the catalytic activity of Na₂WO₄/Al₂O₃ was increased gradually with increasing phosphorus contents up to 2.5 wt.%. The catalyst was recycled and the results show that no significant decrease in catalyst activity was observed even after five recycled runs. We also applied our catalyst in oxidative desulfurization (ODS) of FCC diesel oil (with sulfur contents 4100 ppm), and more than 92% of sulfur was removed from diesel oil under mild reaction conditions.     

High pressure plant for heterogeneous catalytic CO2 hydrogenation reactions in a continuous flow microreactor

The CO₂ hydrogenation to methanol is favored by high pressure from the thermodynamic point of view. Mostly experimental work on this reaction is limited at 400 bar due to technical and safety reasons. In this work we present a high pressure plant able to conduct CO₂ hydrogenation reactions at pressures up to 950 bar in a capillary microreactor; we focus on the influence of pressure concerning process intensification.To validate the plant functionality the reverse water–gas shift (RWGS) reaction was conducted over a 1 wt% Pt/CeO₂ catalyst at 450 °C and between 200 and 950 bar. A mass flow controller for hydrogen was developed due to lack of commercial available hydrogen mass flow controller able to work in the micro liter per minute range and up to 1000 bar. Additional to the RWGS reaction two more reactions take place. The first is the CO disproportionation reaction which results in deposited carbon on the catalyst. The second is the subsequent hydrogenation of carbon to methane. The experimentally determined CO₂ conversion is clearly below the equilibrium of the entire reaction network, hence the reaction is kinetically limited. The reaction performance increases with pressure showing process intensification.     

Kinetic study of CO hydrogenation over co-precipitated iron–nickel catalyst

The kinetic of the Fischer–Tropsch synthesis over a Fe–Ni/Al₂O₃ catalyst was investigated in a fixed bed micro reactor. Experimental conditions were varied as follow: reaction pressure 2–10 bar, H₂/CO feed ratio of 2/1 and space velocity of 96–450 cm³(STP)/h/gram_catalyst at the temperature range 523–573 K. On the basis of carbide-enol mechanism and Langmuir–Hinshelwood–Hougen–Watson (LHHW) type rate equations, seventeen kinetic expressions for CO consumption were tested and interaction between adsorption HCO and dissociated adsorption hydrogen as the controlling step gave the most plausible kinetic model. The activation energy was 46.5 kJ/mole for optimal kinetic model.     

Polyoxometalate as effective catalyst for the deep desulfurization of diesel oil

Aiming at the deep desulfurization of the diesel oil, a comparison of the catalytic effects of several Keggin type POMs, including H₃PW_xMo_12?xO₄₀ (x = 1, 3, 6), Cs_2.5H_0.5PW₁₂O₄₀, and H₃PW₁₂O₄₀, was made, using the solution of DBT in normal octane as simulated diesel oil, H₂O₂ as oxidant, and acetonitrile as extractant. H₃PW₆Mo₆O₄₀ was found to be the best catalyst, with a desulfurization efficiency of 99.79% or higher. Hence, it is promising for the deep desulfurization of actual ODS process. The role of the main factors affecting the process including temperature, O/S molar ratio, initial sulfur concentration, and catalyst dosage, was investigated, whereby the favourable operating conditions were recommended as T = 60 °C, O/S = 15, and a catalyst dosage of 6.93 g (H₃PW₆Mo₆O₄₀)/L (simulated diesel). With the aid of GC–MS analysis, sulfone species was confirmed to be the only product after reaction for 150 min. Furthermore, macro-kinetics of the process catalyzed by H₃PW₆Mo₆O₄₀ was studied, from which the reaction orders were found to be 1.02 to DBT and 0.38 to H₂O₂, and the activation energy of the reaction was found to be 43.3 kJ/mol. Moreover, the catalyst recovered demonstrated almost the same activity as the fresh.     

Selective recovery of valuable metals from partial silicated sphalerite at elevated temperature with sulfuric acid solution

The purpose of this work was to study the feasibility at laboratory-scale of a hydrometallurgical process for the selective recovery of valuable metals from partial silicated sphalerite in an oxygen pressure acid leaching system. The factors influencing dissolution efficiency of the ore were investigated and optimized. Under optimum conditions (i.e., temperature of 433 K, sulfuric acid concentration of 41.2 g/L, leaching time of 2.5 h, liquid/solid ratio of 6 mL/g, and pressure of 1.6 MPa) over 97% Zn was extracted into the leach liquor together with 0.3% SiO₂ and 2.9% Pb. The leaching slurry had good solid–liquid separation characteristics, and the filtration rate could be as high as 716 L/m² h. About 96% oxidation of sulfide sulfur to sulfate was achieved under these conditions. Analysis of the content of elemental sulfur in the leaching residues indicated that the fraction of sulfide sulfur determined as elemental sulfur was about 10% at 393 K, and that it decreased with temperature down to 0.5% at 453 K. Ultimate solid residues, which have been concentrated in silica and lead, can be oriented toward the lead smelter after alkali roasting-water washing pretreatment for metal recovery.     

Continuous experiment regarding hydrogen production by Coal/CaO reaction with steam (II) solid formation

Integration of coal gasification and CO₂ separation reactions in one reactor may produce a high concentration of hydrogen. To design a reactor for this new reaction system, it is necessary to know all reaction behaviors in the integrated reaction system. In our previous study, we performed a continuous reaction experiment of coal/CaO under high steam pressure and confirmed that H₂ concentration higher than 80 vol% with little CH₄ was produced; and that almost all CO₂ was fixed by adding CaO. In this study, the behaviors of solid products during the continuous experiment were investigated. It was found that, CaO first reacted with high-pressure steam to form Ca(OH)₂ (hydration), then the Ca(OH)₂ absorbed the CO₂ generated by coal gasification to form CaCO₃. The hydration of CaO restored sorbent reactivity. Eutectic melting of Ca(OH)₂/CaCO₃ was found to occur in the experiment at 973 K, and this eutectic melting led to the growth of large particles of solid materials. However, at the relatively low temperature of 923 K, eutectic melting could be avoided. Carbon conversion of the coal in the continuous reaction of the coal/CaO mixture with steam was high as 60–80%, even at the lower temperature of 923 K.