合成氨生产中硫化物净化工艺设备选择研究

通过分析硫化物的存在形式、工艺设备条件的选择和小氮肥企业脱硫工艺状况，论述了合成氨工艺中硫化物净化的影响因素和操作中注意的问题。

复合醇胺溶液脱硫脱碳技术研究进展

简要介绍了气体净化领域常用的醇胺溶剂的物理化学性质;综述了技术成熟的醇胺溶液复配种类及典型应用实例;重点归纳了各类复配醇胺溶液在天然气、液化气和炼厂干气、烟道气以及制甲醇与氨的合成气等净化领域的应用及研究情况;指出了醇胺溶液脱硫脱碳技术的应用前景。

硫氧化菌种脱除硫化物生成单质硫限制性因素优化

【目的】针对硫氧化菌种较为特殊的生化特性,优选其氧化硫化物生成单质硫过程的相关限制性因素,以提高该类菌种生成单质硫效率。【方法】采用一株典型脱硫菌Thermithiobacillus tepidarius JNU-2(T.tepidarius JNU-2)氧化硫化物生成单质硫。研究该菌株在以Na2S2O3为能源底物时的培养特性和脱硫性能,并结合单因素实验对菌株氧化硫化物生成单质硫的限制性因素进行优选。【结果】T.tepidarius JNU-2在以Na2S2O3为唯一能源底物培养时的μmax为0.207 h-1,最终生物量为4.0×106 cells/m L。98%的Na2S2O3在24 h时被消耗殆尽,此时单质硫产量达到最大值为0.8 g/L。随后单质硫逐渐被氧化利用,最终稳定在0.2 g/L。经过对该过程主要限制性因素进行单因素实验优化,确定最佳碳氮源、Mg SO4、Fe SO4和能源底物条件分别为:CO2、NH4Cl0.5 g/L、Mg SO4 0.5 g/L、Fe SO4 0.1 g/L和Na2S2O3 15.0 g/L。优化后的氧化Na2S2O3生成单质硫过程的最大生物量可达4.8×106 cells/m L,单质硫产量提升至1.14 g/L。相较于未优化之前,单质硫的产量提高了42.5%。【结论】优化该过程主要限制性因素可有效提高化能自养型T.tepidarius JNU-2氧化硫化物生成单质硫效率。

我国航空燃料精制工艺装备技术进展

我国每年生产 50 0多万 t航空燃料。随着炼油厂高硫、高酸值原油加工比例的不断提高 ,使航空燃料中腐蚀性有害物质的含量也随之增加 ,对飞机的供油系统和发动机燃烧系统产生严重的腐蚀与破坏 ,直接威胁到飞行的安全 ,因此 ,需要将它们从航空燃料中分离出去。为此 ,对目前我国航空燃料精制工艺装备技术进行了较全面的论述和深入的分析 ,结合中国的实际情况和国外发展趋势 。

Interaction of sulfur with iron compounds in sodium aluminate solutions

Reaction behaviors of sulfur and iron compounds in sodium aluminate solutions were investigated. The results show that iron compounds can remarkably remove the S2 but cannot get rid of S2Oc2-, SO^2- and SO4^-2 in sodium aluminate solutions. The removal efficiency of S^2- using ferrous compound and ferric compound can reach 86.10% and 92.70% respectively when the iron compounds were added with a molar ratio of 2：1 compared with the sulfur in liquors at 100℃. Moreover, several same compounds are formed in those two desulfurization processes with ferrous or ferric compounds, including erdite, hematite, amorphous ferrous sulfide, polymerized sulfur-iron compounds and ferric sulfate. The major difference between these two processes is that the erdite generated from ferrous compounds at the initial reaction stage will convert to a sodium-free product FeS2 at the subsequent stage.

Tentative Study on a New Way of Simultaneous Desulfurization and Denitrification

Thiobacillus denitrificans, a kind of autotrophic facultative bacteria, can oxidize sulfide into elemental sulfur or sulfate when nitrate was adopted as its electron accepter and carbon dioxide as its carbon resource under anoxic or anaerobic environment. In this way, nitrate is converted into nitrogen. In addition, ThiobaciWus denitrificans can accumulate sulfur extracellularly. In this study, in a process of simultaneous desulfurization and denitrification, a strain of Thiobacillus denitriificans is employed as sulfur-producer in the treatment of wastewater containing sulfide and nitrate. The key factors affecting this process are investigated through batch tests. The experimental results indicate that the sulfide concentration and the ratio of sulfide to nitrate (S2-/NO3-) in the influent are the key factors, and their suitable values are suggested to be 5/3 and no more than 300mg·L-1, respectively, in order to achieve high conversion of sulfur.

Experimental Research on Flue Gas Desulfurization by Superfine Titanium Dioxied

The mechanism of all present adopted desulfurization technologies is chemical reaction. A new kind of desulfurization medium - TiO 2 particle having large fraction void and specific surface area which is made from TiO 2 with superfine size sintered at low temperature and processed with surface activation is tested and investigated. The mechanism of desulfurization is mainly physical adsorption instead of traditional chemical reaction. Four samples of such TiO 2 particles were characterized by advanced instruments and tested for adsorption dynamics at the temperature range of 90?℃ to 240?℃ in a fixed bed. The results show that its adsorption ability for SO 2in flue gas is dependent strongly on three factors: quality of TiO 2particles, adsorption temperature and SO 2 concentration in flue gas. Titanium dioxide has well desulfurization character and pretty good prospect in engineering application. Sintered at temperature range from 440?℃ to 540?℃, it has the best adsorption ability. In practical use the best adsorption temperature is around 120?℃.

Preparation of Cu-BiVO_4 and Its Photocatalytic Properties for Desulfurization of Model Oil

A photocatalyst Cu-BiVO4 was synthesized by the hydrothermal method and was characterized by XRD, UV-vis DRS, and N2 adsorption-desorption measurement. The catalytic activity of the Cu-BiVO4 samples was studied on desulfurization of thiophene dissolved in n-octane, which was used as a model light oil, via photocatalytic oxidation reaction under illumination by visible light. The catalyst characterization results indicated that the loading of Cu on the catalyst did not change the crystal phase of BiVO4, and the crystallinity of the Cu-BiVO4 sample was found to be better at pH=7. The Cu-BiVO4 samples presented a significant bathochromic shift of the absorption band in the visible region, and the absorption intensity increased for the composite catalyst. The desulfurization experiments showed that the Cu-BiVO4 sample prepared at a pH value of 7 had a better catalytic activity. Under proper operating conditions, the desulfurization rate of the model compound achieved by Cu-BiVO4 sample prepared at pH=7 could reach as high as 90%.

Preparation of Bi_2WO_6 Photocatalyst and Its Application in the Photocatalytic Oxidative Desulfurization

A type of visible light photocatalyst Bi2WO6 was prepared from Bi(NO3)3.5H2O and Na2WO4.2H2O by means of hydrothermal method and was characterized by UV-vis diffuse reflectance spectrometry and XRD.Oxidative desulfurization via photocatalysis was investigated using thiophene dissolved in octane as the model compound,with hydrogen peroxide used as the oxidant.The effects of hydrogen peroxide mass fraction,irradiation time,dosage of photocatalyst Bi2WO6 on the desulfurization efficiency were also investigated.Under suitable conditions,the desulfurization rate of model compound reached over 70%.

Oxidative Desulfurization of Model Sulfur Compound by Potassium Ferrate in the Presence of Phosphomolybdic Acid Catalyst

In this work, the removal of thiophene from simulated oil has been studied by using the adsorption, extraction and oxidation/adsorption methods, respectively. In the adsorptive desulfurization process, different commercial adsorbents were used to eliminate thiophene at ambient pressure and mild temperature, and the results showed that carbon powder had the best adsorption ability. In the extractive desulfurization process, the best desulfurization result was obtained when DMF is used. In the oxidative/adsorptive desulfurization procedure using synthesized potassium ferrate as the oxidant and phosphomolybdic acid solution as the catalyst, thiophene was oxidized and removed from hydrocarbons in combination with active carbon adsorption, and the residual sulfur content of simulated oil could be reduced to 15.3mg/L from the original level of 200mg/L, with the desulfurization rate reaching 92.3%.

Adsorptive Desulfurization of Propylmercaptan and Dimethyl Sulfide by CuBr_2 Modified Bentonite

Adsorptive desulfurization for removing propylmercaptan （PM） and dimethyl sulfide （DMS） over CuBr2 modi- fied bentonite was investigated under ambient conditions in this work. A saturated sulfur capacity as high as 196 mg of S per gram of adsorbent was demonstrated. The influence of loading amount of Cu （II） and calcination temperature on adsorptive desulfurization was investigated. Test results revealed that the optimum loading amount of Cu （II） was 15%, and the calcination temperature was 150 ℃. The pyridine-FTIR spectroscopy showed that a certain amount of Lewis acid could contribute to the increase of adsorption capacity. Spectral shifts of the v（C-S） and v（Cu-S） vibrations were detected from the Raman spectra of the Cu （II） complex which was a reaction product of CuBr2 with DMS. According to the hybrid orbital theory and the complex adsorption reaction, the desulfurization of PM and DMS over the CuBr2 modified bentonite is ascribed to the formation of S-M （σ） bonds.

Removal of Thiophenic Sulfur Compounds from Oil Using Chlorinated Polymers and Lewis Acid Mixture via Adsorption and Friedel-Crafts Alkylation Reaction

For efficient removal of thiophenic sulfur （S-） compounds from oils, a novel method is proposed here, i.e. one-pot alkylation desulfurization （OADS）, in which oil insoluble chlorinated polymer such as polyvinyl chlo- ride （PVC） is used as the alkylating regent with Lewis acid as catalyst. The aromatic S-compounds are grafted to the polymer through Friedel-Crafts reaction and removed facilely along with the polymer. The OADS mechanism is identified by scanning electron microscope and analyzer with surface area and pore size of the polymer. The influ- ence of some factors on the OADS is studied, e.g. the type and amount of chlorinated polymers and Lewis acids. It is nroved that thionhene and benzothioDhene can be removed efficiently from oil by PVC＋AlCl3 mixture even in the presence of 25% （by mass） of benzene due to the synergetic effects of the adsorptive desulfurization of AlCl3 and the alkylation desulfurization of PVC.

Preparing an SbSn intermetallic compound by melt-annealing and application to electric desulfurization of crude oil

We prepared an SbSn intermetallic compound powder with a mixture of equal molar amounts of antimony （Sb） and tin （Sn） by melt-annealing and high-energy ball milling, and characterized the obtained substance with XRD （X-ray diffraction）, DSC （differential scanning calorimetry）, SEM （scanning electron microscopy）, and XPS （X-ray photoelectron spectroscopy）. The prepared SbSn has a hexagonal structure with a melting point of 425 ℃. The particles have a dendritic appearance in micromorphology images. More Sb atoms are enriched on the surface than Sn atoms. A desulfurization efficiency of up to 33.92% can be obtained when applying this powder as a medium in the electric desulfurization of crude oil under the following conditions an emulsion with a volumetric ratio of water to oil at 20：80, a surfactant mass fraction in the emulsion of 0.18%, a processing time of 17 h, and a voltage of 9.68 V. SbSn could be a promising catalyst for desulfurizing crude oil. The desulfurization performance is ascribed to the electron cavities formed by current induction.

Study on Kinetics for Desulfurization of Model Diesel

In this study,by means of the experiments for desulfurization of model diesel through oxidative extraction,the changes associated with the rate of desulfurization of diesel and the mechanism for oxidation of sulfides in diesel were explored. Through studying the mechanism for oxidation of sulfides and the principle of solvent extraction,the kinetic equation of desulfurization via oxidative extraction were determined. By means of the evaluation of model parameters and curve fitting,the reaction order between organic sulfide and sulfone,the intrinsic oxidation rate constant of organic sulfide and sulfone,and the equilibrium constant between sulfone in model diesel and extractive solvent were determined. The experimental values of the desulfurization rate and the theoretical values of the corresponding model equation had closely demonstrated that the desulfurization reaction rate had high accuracy. And the reaction kinetics could provide an important basis for diesel desulfurization process in the future.

Enhanced Performance of Denitrifying Sulfide Removal Process by 1,2-Naphthoquinone-4-Sulphonate

The denitrifying sulfide removal(DSR) process with bio-granules comprising both heterotrophic and autotrophic denitrifiers can simultaneously convert nitrate, sulfide and acetate species into di-nitrogen gas, elemental sulfur and carbon dioxide, respectively, at high loading rates. This study has determined that the reaction rate of sulfide oxidized into sulfur could be enhanced in the presence of 1,2-naphthoquinone-4-sulphonate(NQS). The presence of NQS mitigated the inhibition effects of sulfide species on denitrification. Furthermore, the reaction rates of nitrate and acetate to nitrogen gas and CO_2, respectively, were also promoted in the presence of NQS, thereby enhancing the performance of DSR granules. The advantages and disadvantages of applying the NQS-DSR process are discussed.

Challenges from the New Emission Standards for SO_2 and NO_X

The Emission Standards of Air Pollutants from Thermal Power Plants (GB 13223-2011) prescribe a stricter limitation to air pollutants than ever before. As set in the new emission standard, the limitations of SO2 and NOX for sensitive areas under normal conditions are 50 mg/m3 and 100 mg/m3, respectively. The objective analysis and suggestions are proposed. The recent status and operational experience of desulfurization and denitrification equipment are discussed. From the discussions, thermal power plants face a huge challenge to satisfy the new emission standards. For further reducing of the emission concentrations of SO2 and NOX, three methods were introduced, including: seriously implementing the emission standards, improving treatment equipment, and increasing the efficiencies of desulfurization and denitrification.

Progress in the Technology for Desulfurization of Crude Oil

The poor quality of crude oil obviously leads to high sulfur contents of oil products, and the technology for desulfurization of crude oil is urgently needed so that the sulfur contents in petroleum product could be reduced from the root. This paper describes the progress in technology for desulfurization of crude oil. The present technologies for desulfurization of crude oil include caustic washing, dry gas desulfurization, hydrodesulfurization （HDS）, etc. The new combined technologies for desulfurization of crude oil being studied are： biodesulfurization （BDS）, hydrogenationbacterial catalysis, the microwave-catalytic hydrogenation, the BDS-OD-RA desulfurization and oxidative desulfurization in electrostatic fields, and the ultrasonic/microwave-catalytic oxidation applied in our lab, with their development trends being also discussed.

Effect of Mixed Oxide Support for Ni/ZnO in Reactive Adsorption Desulfurization

The effect of mixed oxide support on the performance of Ni/ZnO in the reactive adsorption desulfurization(RADS) reaction was investigated in a fixed bed reactor by using thiophene as the sulfur-containing compound in the model gasoline. A series of oxide supports for Ni/ZnO were synthesized by the co-precipitation method and characterized by XRD, N_2-adsorption, TPR and NH_3-TPD techniques. It was found that the desulfurization capacity of Ni/ZnO was enhanced greatly when active components were supported on the proper mixed oxide. Ni/ZnO supported on oxides exhibited much higher desulfurization efficiency and sulfur adsorption capacity than the unsupported Ni/ZnO and the synthesized Ni/ZnO-SA adsorbent exhibited the highest efficiency for thiophene removal. The higher desulfurization activity and sulfur capacity of Ni/ZnO supported on SiO_2-Al_2O_3 with small particle size, high specific surface area and large pore volume could promote the high dispersion of active metal phase and the transfer of sulfur to ZnO with lower mass transfer resistance. γ-Al_2O_3 species could weaken the interaction of active phases and SiO_2 as well as could increase greatly the amount of weak acids. Therefore, these oxides could impose a great influence on the structure and chemical properties of the catalyst.

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.