器外完全硫化态选择性加氢脱硫催化剂硫化工艺条件的优化

考察了硫化温度、硫化氢质量分数、硫化压力等工艺条件对器外完全硫化态选择性加氢脱硫催化剂性能的影响,并对硫化工艺进行了优化。结果表明:采用气相成膜微钝化技术对器外完全硫化态选择性加氢脱硫催化剂进行处理,可较好地解决其与空气接触时性能不稳定的问题;在硫化温度为350℃,硫化氢质量分数为0.3%,硫化压力为0.5 MPa的较佳条件下,制得的器外完全硫化态选择性加氢脱硫催化剂,与常规器内硫化态选择性加氢脱硫催化剂相比,其选择因子可提高31%。

船舶尾气脱硫装置脱硫滞后性监测分析

2020“限硫令”的实施对航运业产生了重大影响,部分船舶采取安装尾气脱硫装置作为替代措施。为推动解决海事部门对安装脱硫装置船舶尾气排放合规性的监管难题,通过研究大型集装箱船舶“C”轮的脱硫装置和船舶尾气排放在线监测数据,验证了尾气在线监测数据的可靠性和规律性,发现脱硫装置存在脱硫滞后性。因此,可用船舶尾气在线监测数据验证外部遥感技术监测尾气排放数据的准确性,同时可用于指导尾气脱硫装置及尾气排放合规性的现场监管。

还原剂法强化煤浮选脱硫的研究

为了拓宽电化学法在煤脱硫中的应用,研究了还原剂法脱硫的几个影响因素及其脱硫机理,利用X射线衍射对还原剂法处理前后的黄铁矿样进行了分析。结果表明:影响还原剂法脱硫的因素的次序为反应时间>pH值>还原剂用量>反应温度;确定了最佳反应条件,反应时间为20 min,pH=6.65,还原剂(连苯三酚)用量为75 mg,反应温度为30℃;在较优实验条件下,其脱硫率可达到60%。研究表明,还原剂法能使煤与黄铁矿颗粒表面朝不同的方向改性:提高了煤的可浮性,降低了黄铁矿的可浮性;同时还原剂法还能改善煤质,提高煤的燃烧值。

Effect of integration of mechanical ball milling and flue gas desulfurization gypsum on dealkalization of bauxite residue

The synergistic impact of mechanical ball milling and flue gas desulfurization(FGD)gypsum on the dealkalization of bauxite residue was investigated through integrated analyses of solution chemistry,mineralogy,and microtopography.The results showed a significant decrease in Na_(2)O content(>30 wt.%)of FGD gypsum-treated bauxite residue after 30 min of mechanical ball milling.Mechanical ball milling resulted in differentiation of the elemental distribution,modification of the minerals in crystalline structure,and promotion in the dissolution of alkaline minerals,thus enhancing the acid neutralization capacity of bauxite residue.5 wt.%FGD gypsum combined with 30 min mechanical ball milling was optimal for the dealkalization of bauxite residue.

Modification of Activated Carbon Fiber by Loading Metals and Their Performance on SO2 Removal

Metal-loaded activated carbon fibers （ACFs） were prepared by impregnation and characterized by N2 adsorption at 77K, XRD, XPS and SEM. Their properties on SO2 removal were examined in a tubular fixed bed reactor with a model flue gas. Cobalt-loaded ACF showed the best activity among the prepared metal-loaded ACFs and a constant removal ratio of SO2 above 87% during continuous exposure to the flow of SO2/O2/H2O/N2 at 45℃ for more than 216h. The characteristic of the prepared loaded-ACFs showed that the exceptional activity of Co-ACF was attributed to the high amount of active sites due to modification by loading cobalt.

Study on Relationship between Microstructure of Active Phase and HDS Performance of Sulfided Ni-Mo Catalysts: Effect of Metal Loading

Six Ni-Mo catalysts with different metal contents were prepared and characterized by N2 adsorption and X-ray diffi＇actometry. The active phase microstructure of these catalysts was examined by the Raman spectroscopy, temperature- programmed reduction （TPR）, X-ray photoelectron spectroscopy, and high-resolution transmission electron microscopy. Hydrodesulfurization （HDS） activity of catalyst samples were analyzed in a flow fixed-bed microreactor. The sulfidation degree of Mo and the length of the MoS2 slab slightly increased with the amount of metal loaded following sulfidation. This small change is attributed to polymolybdate species observed in all the oxidized catalysts. Weak metal-support interactions, as determined by the TPR technique, increased the NiSx sulfidation phase and MoS2 slab stacking. The HDS activity of the catalyst samples increased with the number of active sites. For high metal loading catalysts, their HDS activity was nearly identical because the sulfur atoms cannot easily approach active sites. This change is caused by the large number of stacked layers in the MoS2 slabs as well as the decrease in the specific surface area and pore volume of the catalyst samples with an increasing metal loading.

Effect of the surface properties of an activated coke on its desulphurization performance

Commercial coke was modified by H2O2 and/or NH3.H2O to obtain an activated coke containing additional oxygen functional groups and/or nitrogen functional groups. The aim of the modification was to enhance the SO2 adsorption capacity of the activated coke. Several techniques, including total nitrogen content measurements, SO2 adsorption, XPS and FTIR analysis, were used to characterize the coke samples. The XPS and FTIR spectra suggest the existence of -CONH2 groups in the H2O2 plus ammonia modified coke. The SO2 adsorption capacity of an activated coke increases slightly with an increase in H2O2 concentration during the modification process. The desulphurization performance of a modified coke is considerably enhanced by increasing the treatment temperature during ammonia modification. The amount of nitrogen in a coke modified by H2O2 plus NH3.H2O is the highest, and the SO2 adsorption capacity of the coke is also the highest (89.9 mg/gC). The NH3.H2O (only) modified sample has lower nitrogen content and lower desulphurization capacity (79.9 mg/gC). H2O modification gives the lowest SO2 adsorption capacity (28.9 mg/gC). The H2O2 pre-treatment is beneficial for the introduction of nitrogen onto the surface of a sample during the following ammonia treatment process.

Preparation, Characterization, Hydrodesulfurization and Hydrodenitrogenation Activities of Alumina-supported Tungsten Phosphide Catalysts

Two series of WP/Al2O3 catalyst precursors with WP mass loading in the range 18.5%—37.1% were prepared using the impregnation method and mixing method, respectively, and the catalysts were then obtained by temperature-programmed reduction of supported tungsten phosphate (precursor of WP/Al2O3 catatlysts) in H2 at 650℃ for 4h. The catalysts were characterized by XRD, BET, TG/DTA , XPS and 31P MAS-NMR. The activities of these catalysts were tested in the hydrodenitrogenation (HDN) of pyridine and hydrodesulfurization (HDS) of thiophene at 340℃ and 3.0MPa. The results showed that owing to the stronger interaction of the support with the active species, the precursor of WP/Al2O3 catalyst was more difficultly phosphided and a greater amount of W spe- cies was in a high valence state W6+ on the surface of the catalyst prepared by the impregnation method than that by the mixing method. 31P MAS-NMR results indicated that 31P shift from 85% H3PO4 of 2.55×10-4 for WP and 2.57 ×10-4 for WP/γ-Al2O3 catalysts prepared by mixing method. Such WP/Al2O3 catalysts showed higher HDN activi- ties and lower HDS activities than those prepared by the impregnation method under the same loading of WP. WP/γ-Al2O3 catalysts with weak interaction between support and active species were favorable for HDN reaction while the WP/γ-Al2O3 catalysts with strong interaction were favorable for HDS reaction.

Influence of Carbon Content on S Zorb Sorbent Activity

The reaction activity of S Zorb sorbents with different sulfur contents was investigated, and the structure and composition of carbon-containing sorbents were characterized by XRD, FT-IR and TG-MS in order to delve into the kind and morphology of carbon on the sorbent. Test results have revealed that coke could be deposited on the S Zorb sorbent during the operating process, and the coke content was an important factor influencing the reaction performance of the S Zorb sorbent. Retention of a definite amount of coke on the sorbent while securing the desulfurization activity of the S Zorb sorbent would be conducive to the reduction of octane loss of reaction product.

Effects of Soluble Ions on Hydration of Calcined Flue Gas Desulphurization Gypsum

The influence of various water soluble cations(K^+,Na^+,Ca^2+,Mg^2+)on the hydration of calcined flue gas desulphurization gypsum was investigated.The results show that all cations but Ca^2+can accelerate the hydration of bassanite.The final crystal size is not largely influenced by different salts,except for Na^+,where the giant crystal with length of>130μm is observed.Current study clarifies the influence of different ions on the hydration of bassanite,which could provide sufficient guide for the pre-treatment of original flue gas desulphurization gypsum before actual application.

Deep Hydrodesulfurization of Diesel Fuel over Diatomite-dispersed NiMoW Sulfide Catalyst

Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products obtained over different catalysts were determined by GC-PFPD.The test results showed that the diatomite-dispersed NiMoW catalyst had high hydrodesulfurization activity for FCC diesel,which could be contributed to the excellent hydrogenation performance of the said catalyst.Characterization of catalyst by TEM and XRD indicated that the diatomite-dispersed NiMoW catalyst possessed higher layer stacking,larger curvature of MoS2or WS2,and segregated Ni3S2crystals relative to the supported catalyst.This kind of structure leads to high hydrogenation activity of the diatomite-dispersed NiMoW catalyst.

Investigation on Modification of NaY Zeolite and Its Behaviors in Selective Adsorptive Desulfurization of FCC gasoline

NaY zeolite was modified with oxalic acid, and Ce(IV)Y(1) zeolite was obtained via liquid phase ion exchange between the modified NaY zeolite and cerium nitrate. The Ce(IV)Y(2) zeolite was obtained via liquid phase ion exchange between NaY zeolite and cerium nitrate. The performance of two Y zeolites [Ce(IV)Y(1) and Ce(IV)Y(2)] was compared through static selective adsorptive desulfurization of FCC gasoline at room temperature and normal pressure. The sulfur compounds and contents of the FCC gasoline were analyzed by microcoulometry and GC-SCD chromatogram. The results showed that the effect of adsorptive desulfurization of FCC gasoline achieved by Ce(IV)Y(1) zeolite was better than that of Ce(IV)Y(2) zeolite. The rate for adsorptive desulfurization of FCC gasoline by Ce(IV)Y(1) zeolite and Ce(IV)Y(2) zeolite was 85.0% and 62.4%, respectively. The Ce(IV)Y(1) zeolite could adsorb DMTs, which could not be adsorbed by Ce(IV)Y(2) zeolite. The rate of regeneration of extruded Ce(IV)Y(1)zeolite was 95.5%.

Design of the Metal Precursors Molecular Structures in Impregnating Solutions for Preparation of Efficient Ni Mo/Al_2O_3 Hydrodesulfurization Catalysts

The molecular structures of metal precursors in the impregnating solution were designed so as to prepare efficient Ni Mo/Al_2O_3 hydrodesulfurization(HDS) catalysts. At first, five typical impregnating solutions were designed; the existing metal precursors, such as [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species in the solutions were confirmed by laser Raman spectroscopy(LRS). The UV-Vis spectra results indicated that the solutions containing both phosphoric acid and citric acid could change the existing form of nickel species. Five corresponding Ni Mo/Al_2O_3 catalysts were prepared by the incipient wetness impregnation method. The LRS analysis results of dried catalysts showed that the above metal precursors could be partly retained on alumina support after impregnation and drying, although the interface reaction between different metal precursors and alumina support unavoidably took place. Then the catalysts were sulfided and characterized by N2 physisorption, TEM and XPS analyses. The results showed that different metal precursors in impregnating solution could mainly result in the difference in both the morphology of(Ni)Mo S2 slabs and the promoting effect of Ni species. The catalyst prepared mainly with [P2Mo5O23]^(6-)-like species used as precursors exhibited worse dispersion of(Ni)Mo S2 slabs and lower ratio of Ni–Mo–S active phases than the one with [Mo4(citrate)2O11]^(4-)-like species. Promisingly, the catalyst prepared with co-existing [Mo4(citrate)2O11]^(4-)-like, [P2Mo18O62]^(6-)-like and [P2Mo5O23]^(6-)-like species showed better hydrodesulfurization activity for 4,6-DMDBT thanks to its more well-dispersed Ni–Mo–S active phases.

Application of Modified Attapulgite Clay as the Adsorbent in Gasoline Desulfurization

Attapulgite clay is a kind of special silicate mineral with high adsorption capacity thanks to its loose structure and porous surface. In this paper, the attapulgite clay was treated effectively with acid under microwave thermal activation and ultrasonic vibration, respectively, and characterized by XRD, N2 adsorption, FT-IR and SEM. The desulfurization performance of the modified attapulgite clay was then evaluated by using simulated gasoline as the feed. The test results showed that the thiophene removal rate increased with an increasing dosage of hydrochloric acid during microwave modification of attapulgite clay. When the concentration of hydrochloric acid reached 15%, the increase of desulfurization rate became slower, and the desulfurization rate was about 69%.

Changes in sulfur form during coal desulfurization with microwave:Effect on coal properties

The changes in sulfur form in coal were analyzed by sulfur K-XANES(K-edge X-ray absorption near edge structures) spectra before and after the coal microwave desulfurization in a Na OH solution. After the desulfurization, the pyritic sulfur content of coal decreased significantly from 53.6% to 39.2%, while the sulfate sulfur content increased from 17.3% to 34.6%. Only a small amount of thiophene sulfur(20.1–16.1%) was removed. Some sulfur-containing components were oxidized to sulfate sulfur. Under the optimum conditions, the ash content decreased, while the volatile content increased. The calorific value of coal slightly decreased with a slight variation in the amplitudes. The overall structure of coal did not change significantly based on Fourier transform infrared(FTIR) spectral analyses. Thus, the desulfurization of coal with microwave irradiation in a Na OH solution did not significantly change the properties of coal.

Thermodynamics and kinetics of fluoride removal from simulated zinc sulfate solution by La(Ⅲ)-modified zeolite

To understand the mechanism of fluoride removal from the simulated zinc sulfate solution by the La(III)-modified zeolite,the adsorbent was characterized by XRD,SEM and EDS.The effects of absorbent dose and contact time,the adsorption isotherms and the sorption kinetics were investigated.The experimental results were compatible with the Langmuir isotherm model.The theoretical maximum adsorption capacities are 20.83 and 23.04 mg/g at 303 and 313 K,respectively.And the physisorption is revealed using the Temkin isotherm model and the D-R isotherm model.The sorption process is more suitable by the pseudo-second-order kinetic models.Thermodynamic parameters such as standard free energy change(ΔGΘ<0 kJ/mol),standard enthalpy change(ΔHΘ=8.28 kJ/mol)and standard entropy change(ΔSΘ=0.030 kJ/(mol?K))indicate the spontaneity of adsorption and endothermic physical sorption.Furthermore,the fluoride concentration in the industrial zinc sulfate solution decreases from 98.05 to 44.09 mg/L with the adsorbent dosage of 15 g/L.

Washability analysis of high sulfur coal gangue from a coal mine in Guizhou

Fulfill the screen test and float-and-sink analysis for high sulfur coal gangue from a Guizhou coal mine, analyzed the washability of its tail coal. Seen from the results： most of sulfur in sample is pyrite, the sulfur content of different particle classification shall be reduced with the decreasing of size and specific gravity, most of sulfur distributed in the coal particles with large-size and high specific gravity. Part of sulfur may be eliminated through special gravity separation, however, most of inorganic sulfur should be removed with the combination of floatation process.

Study on Oxidative Desulfurization Performance of Mesoporous Alumina Material

This article refers to the study on the performance of mesoporous silica used as the catalyst for oxidative desulfurization reactions. The test results revealed that under mild reaction conditions using tert-butyl hydroperoxide as the oxidizing agent the content of dibenzothiophene(DBT) contained in oil samples could be reduced from 5000 ppm to less than 5 ppm. Furthermore,the mesoporous silica material can be easily regenerated and recycled.

Fractal desulfurization kinetics of high-sulfur coal

The pore structure characteristics of high-sulfur coal from Wansheng in Chongqing have been studied by a nitrogen adsorption method （BET）. The effects of grinding and pre-treating with nitric acid on the inorganic sulfur content of coal have been investigated. Organic sulfur in coal pretreated with nitric acid was desulfurized by using propylene-glycol-KOH （PG-KOH）. Fractal kinetic properties of these two desulfurization procedures were investigated by using fractal geometric theory. The results show that both the specific surface area and pore volume increased with the decrease in particle diameter. The microspore surface of coal had fractal characteristics; the fractal dimension was 2.48. The sulfur content decreased with the decrease in particle diameter by grinding. After pretreatment with nitric acid, the desulfurization ratio （DFR） of inorganic sulfur increased to over 99% and the DFR of total sulfur to over 70%. The desulfurization procedure of inorganic sulfur had fractal kinetic characteristics; its reactive frac- tal dimension was 2.94. The organic sulfur desulfurization procedure by PG-KOH was also tallied with fractal kinetic properties; the reactive fracta! dimension was 2.57. The effect of temperature on the desul- furization ratio of organic sulfur can be described with an Arrhenius empirical equation. The rate constant, pre-exponential factor and the activation energy of the reaction increased with the decrease in particle diameter.

Development and CommercialApplication of RSDS-II Technology for Selective Hydrodesulfurization of FCC Naphtha

The FCC naphtha selective hydrodesulfurization technology(RSDS-II)has been tested with different feedstocks in pilot scale.The results show that RSDS-II technology is viable in terms of its adaptability to different feedstocks.To produce gasoline with a sulfur content of less than 50μg/g by the RSDS-II technology,the gasoline RON loss is less than 1.8,0.9and 0.2 units,respectively,upon processing the conventional high-sulfur and high-olefin FCC naphtha,the high-sulfur MIP naphtha,and the medium-sulfur or low-sulfur MIP naphtha.Upon using the naphtha produced from pre-hydrotreated FCC feedstock as the RSDS-II feedstock to manufacture gasoline with a sulfur content of lower than 10μg/g,the RON loss does not exceed 1.0 unit.The RSDS-II technology has been commercialized successfully at many refineries.The result of operating commercial RSDS-II unit at the Shanghai Petrochemical Company has revealed that upon processing a feedstock containing 38.7 v% —43.3 v% of olefins and 250—470 mg/g of sulfur,the sulfur content in the treated gasoline ranges from 33μg/g to 46μg/g and the RON loss is equal to only 0.3—0.6 units.Till now this RSDS-II unit has been operating smoothly over 30 months.Thanks to its high HDS activity and good selectivity,the RSDS-II technology can meet the refinery’s needs for adequate upgrading of gasoline.